CN105198048A - Three-dimensional electrode filling material and preparation method thereof - Google Patents
Three-dimensional electrode filling material and preparation method thereof Download PDFInfo
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- CN105198048A CN105198048A CN201510705791.2A CN201510705791A CN105198048A CN 105198048 A CN105198048 A CN 105198048A CN 201510705791 A CN201510705791 A CN 201510705791A CN 105198048 A CN105198048 A CN 105198048A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title abstract description 17
- 238000011049 filling Methods 0.000 title abstract 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910052742 iron Inorganic materials 0.000 claims abstract description 52
- 238000007747 plating Methods 0.000 claims abstract description 31
- 239000004927 clay Substances 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 11
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 19
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 13
- 239000005995 Aluminium silicate Substances 0.000 claims description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims description 12
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 235000003642 hunger Nutrition 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- 230000037351 starvation Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 5
- 229940038773 trisodium citrate Drugs 0.000 claims description 5
- 229960004418 trolamine Drugs 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 50
- 239000002351 wastewater Substances 0.000 abstract description 16
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 238000006731 degradation reaction Methods 0.000 abstract description 15
- 230000004913 activation Effects 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000002955 isolation Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 230000000593 degrading effect Effects 0.000 description 6
- 238000004064 recycling Methods 0.000 description 5
- -1 after bonding Chemical compound 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 206010041954 Starvation Diseases 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000003245 working effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010019332 Heat exhaustion Diseases 0.000 description 1
- 206010019345 Heat stroke Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a three-dimensional electrode filling material and a preparation method thereof. The preparation method mainly comprises the following steps: subjecting iron filings to activation including oil removal and rust removal, copper plating and nickel plating so as to obtain improved iron filings; and uniformly mixing the improved iron filings obtained after nickel plating with powdery active carbon and mixed clay in proportion so as to prepare a granular filling material with a diameter of 5 to 10 mm, drying the granular filling material, sintering the granular filling material at 600 DEG C for 2 h under the condition of isolation of oxygen and then carrying out cooling so as to obtain the three-dimensional electrode filling material. The main characteristic of the three-dimensional electrode filling material is that the surfaces of the iron filings are plated with a stable nickel coating, which enables the service life of the iron-carbon filling material to be substantially prolonged. When the three-dimensional electrode filling material is used to treat waste water containing phenol, the degradation rate of phenol is more than 80%, and biodegradability of a water sample is greatly improved. When a recovered three-dimensional electrode filling material is repeatedly used, the degradation rate of phenol can also reach more than 60%, so waste water treatment cost is reduced.
Description
Technical field
The present invention relates to electrode filler, particularly a kind of three-diemsnional electrode filler and preparation method thereof.
Background technology
Phenol is a kind of important industrial chemicals, and in chemical industry, tool has been widely used, but has carinogenicity and mutagenicity due to it, is classified as priority pollutant by U.S. EPA and China.Therefore, the discharge of any wastewater containing phenol all should be strictly controlled.Wastewater containing phenol and comprised charcoal absorption by the minimizing technology of its polluted underground water, polymer resin adsorbs, steam, air peel off, biological degradation and heat collapse etc.Although these method removal efficiency are higher, have that energy consumption is large, cost is high and the problem such as organic efficiency is low.In the last few years, three-dimensional electrolysis technology became important industrial wastewater pollution control techniques day by day due to features such as treatment effect are good, technique is simple, suitability is extensive.
Three-dimensional electrolysis technology is the one in electrochemistry sewage disposal technology, and in three-dimensional electrolysis technology, three-diemsnional electrode filler is the core of this technology, the selection of filler material and preparation, has critical impact to the removal effect of pollutent and operation stability.Current three-diemsnional electrode filler is in the majority with iron carbon filler, but the experimental results shows, there is many defects in the application in this filler, this electrolysis material is after operation for some time, and material surface can form passive film, and material easily lumps simultaneously, thus hinder material to contact with the effective of waste water, cause electrolysis material utilization ratio low, the treatment effect of waste water is declined rapidly, adds the cost of wastewater treatment.Greatly limit the application of three-dimensional electrolysis technology.Therefore, novel three-dimensional electrolysis material that is high-effect, stable, that can repeat to recycle is developed significant for popularization three-dimensional electrolysis technology.
Summary of the invention
In order to overcome defect existing in prior art, the invention provides a kind of three-diemsnional electrode filler and being used as a kind of novel three-diemsnional electrode filler.It has that stability is high, corrosion-resistant, intensity is large, active high, water is stained without secondary, the feature of long service life, provide good scheme for solving in three-dimensional electrolysis reaction the problems such as filler easily hardens, work-ing life is short, perishable.By to the zinc-plated process of the copper facing of Industry Waste iron filings, with itself and gac and clay for raw material, a kind of novel three-dimensional electrolysis filler has been prepared through roasting, with under the environment that is subjects containing phenols simulated wastewater, not only effectively reduce the COD (chemical oxygen demand (COD)) in sewage, improve the biodegradability of waste water, and still have good degradation effect when repeatedly reusing.
A kind of three-diemsnional electrode filler of the present invention and preparation method thereof is achieved through the following technical solutions:
A kind of three-diemsnional electrode filler, component and each constituent mass per-cent of described three-diemsnional electrode filler are as follows: improvement iron filings 10%-25%, gac 35%-50% and mixing clay 30%-45%; And
Described mixing clay is that the kaolin of 85%-95% and the wilkinite of 5%-15% form by mass percent.
Further, described three-diemsnional electrode filler is made up of the component that mass percent is following: improvement iron filings 25%, gac 37.5% and mixing clay 37.5%; And
Described mixing clay is that the kaolin of 90% and the wilkinite of 10% form by mass percent.
Further, described three-diemsnional electrode filler is made up of the component that mass percent is following: improvement iron filings 15%, gac 45% and mixing clay 40%; And
Described mixing clay is that the kaolin of 89% and the wilkinite of 11% form by mass percent.
Further, described three-diemsnional electrode filler is made up of the component that mass percent is following: improvement iron filings 22%, gac 44% and mixing clay 34%; And
Described mixing clay is that the kaolin of 91% and the wilkinite of 9% form by mass percent.
Prepare a method for three-diemsnional electrode filler, comprise the following steps:
Step one: preparation improvement iron filings, its concrete steps comprise:
The iron filings of 0.5-2mm are put into the sodium hydroxide solution of 5%-15% by oil removing, and heating at 50 DEG C-80 DEG C is also filtered after supersound process 40min-100min;
Rust cleaning, will filter after dilute sulphuric acid that gained iron filings are placed in 5%-20% soaks 10-30min and filter through oil removal treatment;
Copper facing, will filter the copper-bath that gained iron filings are placed in 3%-7%, reacting by heating 60min at 40-60 DEG C through processing of rust removing, filters, dry, roasting 4 hours under starvation at 500 DEG C; And
Nickel plating, will be soaked in nickel-plating liquid through copper plating treatment gained iron filings, under ultrasound condition, heat 40 ~ 60 DEG C of 40min, filter, with distilled water wash 3 times, dry, and at 600 DEG C-800 DEG C, isolated air roasting 4 hours, obtains improveing iron filings;
Step 2: by described improvement iron filings, gac and the mass percent Homogeneous phase mixing mixing clay 10%-25%, 35%-50% and 30%-45%, add water in the mixture, shaken the particulate state making diameter 3-5mm;
Step 3: by described granular iron carbon filler 60 DEG C of vacuum dryings, put into retort furnace, add thermal bake-out 2-4 hour under the condition of isolating oxygen, obtained specific surface area is 0.4-1.0m
2the three-diemsnional electrode filler of/g.
Further, the preparation of described nickel-plating liquid comprises the following steps:
Step one: the nickel sulfate solution of the 3%-6% of preparation 500ml, adds Trisodium Citrate 25 ~ 40g, trolamine 15 ~ 20g successively;
Step 2: add 30 ~ 50g sodium hypophosphite solid under agitation, stirring and dissolving;
Step 3: being under agitation adjusted to pH with 10% sodium hydroxide solution is 8; And
Step 4: filter, obtain described nickel-plating liquid.
Owing to adopting above technical scheme, the present invention compared with prior art tool has the following advantages:
1. improve iron filings surface and adopt copper-plating technique, substantially improve the ductility of iron filings;
2. improve iron filings surface and adopt nickel plating technology, define stable, corrosion resistant nickel coating on surface, substantially prolongs its work-ing life;
3. mix clay to mix by a certain percentage primarily of kaolin and wilkinite, after bonding, wilkinite has certain expansion, forms space not of uniform size, add the specific surface area of filler to a certain extent after calcining;
4. after adopting the three-diemsnional electrode filler process wastewater containing phenol 200min for preparing of method of the present invention, degradation rate higher than 80%, far above 50% of conventional iron carbon filler;
5. three-diemsnional electrode filler of the present invention can be recycled, the three-diemsnional electrode filler of recycling to the degradation rate of wastewater containing phenol higher than 70%, after repeatedly Reusability, still can realize the degradation rate higher than 60%, effectively improve the utilization ratio of iron carbon filler.
Accompanying drawing explanation
Fig. 1 is to the degradation rate time history plot of wastewater containing phenol according to three-diemsnional electrode filler of the present invention and conventional iron carbon filler.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
Be the sodium hydroxide solution that the iron filings 200g of 0.5-2mm puts into 15% by diameter, heating at 60 DEG C is also filtered, so that oil removing after supersound process 40min.Gained solid filters, to eliminate rust with after the dilute sulphuric acid immersion 30min of 10%.Above-mentioned oil removing and processing of rust removing are referred to as carries out activation treatment to iron filings.Iron filings after activation are placed in the copper-bath of 5%, reacting by heating 60min at 60 DEG C, filter, dry, roasting 4 hours under 500 DEG C of starvations subsequently.Cooled iron filings are soaked in the 1000mL nickel-plating liquid configured, under ultrasound condition, heat 50 DEG C) nickel plating 40min, filter, with distilled water wash 3 times, dry, at 800 DEG C, isolated air roasting 4 hours, obtains improveing iron filings.The step wherein configuring nickel-plating liquid comprises: the nickel sulfate solution preparing 3% of 500ml, add Trisodium Citrate 20g, trolamine 11g successively, add sodium hypophosphite solid 26g under agitation, stirring and dissolving, then being under agitation adjusted to pH with 10% sodium hydroxide is 8, filter, obtain nickel-plating liquid.
By obtain through activation treatment and plating copper and nickel process improvement iron filings, activity charcoal powder, mixing clay in the ratio of 2:3:3---i.e. mass percent improvement iron filings 25%, gac 37.5% and mixing clay 37.5%---Homogeneous phase mixing, wherein, mix clay to be made up of the kaolin of 90% and the wilkinite of 10%.In said mixture, add a small amount of water, shake the particulate state making diameter 3-5mm, 60 DEG C of vacuum dryings, put into retort furnace, add thermal bake-out 4 hours under the condition of isolating oxygen, and cooling obtains three-diemsnional electrode filler.
In order to check the ability of three-diemsnional electrode filler process wastewater containing phenol, with graphite cake (surface-area 50cm
2) be negative plate, DSA electrode (surface-area 50cm
2) be anode material, the sodium sulfate of 1000mg/L is ionogen, and interelectrode distance is 7cm, and electrolysis time is 60 ~ 120min minute, current density: 60mAcm
-2, at the temperature of 40 DEG C, use the oxybenzene compound aqueous solution that the present embodiment gained three-diemsnional electrode filler degraded concentration is 2500mg/L, under the condition of pH=8, electrolysis time is 100min, and phenol degrading rate is 84%.By reacting liquid filtering, washing and recycling three-diemsnional electrode filler, again with above-mentioned electrolytic condition electrolytic reaction 100min, phenol degrading rate is 80%.Third time, when repeating this step, the degradation rate of phenol was 79%.
Embodiment 2
Be the sodium hydroxide solution that the iron filings 200g of 0.5-2mm puts into 10% by diameter, heating at 60 DEG C is also filtered, so that oil removing after supersound process 40min.Gained solid filters, to eliminate rust with after the dilute sulphuric acid immersion 30min of 10%.Above-mentioned oil removing and processing of rust removing are referred to as carries out activation treatment to iron filings.Iron filings after activation are placed in the copper-bath of 5%, reacting by heating 60min at 60 DEG C, filter, dry, roasting 4 hours under 500 DEG C of starvations subsequently.Be soaked in by cooled iron filings in the 1000mL nickel-plating liquid configured, under ultrasound condition, heat 50 DEG C of nickel plating 40min, filter, with distilled water wash 3 times, dry, at 800 DEG C, isolated air roasting 4 hours, obtains improveing iron filings.The step wherein configuring nickel-plating liquid comprises: the step wherein configuring nickel-plating liquid comprises: the nickel sulfate solution preparing 5% of 500ml, adds Trisodium Citrate 30g, trolamine 18g successively; Add 42g sodium hypophosphite solid under agitation, stirring and dissolving, being then under agitation adjusted to pH with 10% sodium hydroxide is 8, filters, obtains nickel-plating liquid.
By obtain through activation treatment and plating copper and nickel process improvement iron filings, activity charcoal powder, mixing clay in the ratio of 1:3:2.5---i.e. mass percent improvement iron filings 15%, gac 45% and mixing clay 40%---Homogeneous phase mixing, wherein, mix clay to be made up of the kaolin of 89% and the wilkinite of 11%.In said mixture, add a small amount of water, shake the particulate state making diameter 3-5mm, 60 DEG C of vacuum dryings, put into retort furnace, add thermal bake-out 4 hours under the condition of isolating oxygen, and cooling obtains three-diemsnional electrode filler.
In order to check the ability of three-diemsnional electrode filler process wastewater containing phenol, with graphite cake (surface-area 50cm
2) be negative plate, DSA electrode (surface-area 50cm
2) be anode material, the sodium sulfate of 1000mg/L is ionogen, and interelectrode distance is 7cm, and electrolysis time is 60 ~ 120min minute, current density: 60mAcm
-2, at the temperature of 40 DEG C, use the oxybenzene compound aqueous solution that the present embodiment gained three-diemsnional electrode filler degraded concentration is 2500mg/L, under the condition of pH=8, electrolysis time is 100min, and phenol degrading rate is 78%.By reacting liquid filtering, washing and recycling three-diemsnional electrode filler, again with above-mentioned electrolytic condition electrolytic reaction 100min, phenol degrading rate is 76%.Third time, when repeating this step, the degradation rate of phenol was 72%.
Embodiment 3
Be the sodium hydroxide solution that the iron filings 200g of 0.5-2mm puts into 10% by diameter, heating at 60 DEG C is also filtered, so that oil removing after supersound process 40min.Gained solid filters, to eliminate rust with after the dilute sulphuric acid immersion 30min of 10%.Above-mentioned oil removing and processing of rust removing are referred to as carries out activation treatment to iron filings.Iron filings after activation are placed in the copper-bath of 5%, reacting by heating 60min at 60 DEG C, filter, dry, roasting 4 hours under 500 DEG C of starvations subsequently.Be soaked in by cooled iron filings in the 1000mL nickel-plating liquid configured, under ultrasound condition, heat 40 DEG C of nickel plating 40min, filter, with distilled water wash 3 times, dry, at 700 DEG C, isolated air roasting 4 hours, obtains improveing iron filings.The step wherein configuring nickel-plating liquid comprises: the nickel sulfate solution preparing 5% of 500ml, adds Trisodium Citrate 30g, trolamine 18g successively; Add 42g sodium hypophosphite solid under agitation, stirring and dissolving, being then under agitation adjusted to pH with 10% sodium hydroxide is 8, filters, obtains nickel-plating liquid.
By obtain through activation treatment and plating copper and nickel process improvement iron filings, activity charcoal powder, mixing clay in the ratio of 2:4:3---i.e. mass percent improvement iron filings 22%, gac 44% and mixing clay 34%---Homogeneous phase mixing, wherein, mix clay to be made up of the kaolin of 91% and the wilkinite of 9%.In said mixture, add a small amount of water, shake the particulate state making diameter 3-5mm, 60 DEG C of vacuum dryings, put into retort furnace, add thermal bake-out 4 hours under the condition of isolating oxygen, and cooling obtains three-diemsnional electrode filler.
In order to check the ability of three-diemsnional electrode filler process wastewater containing phenol, with graphite cake (surface-area 50cm
2) be negative plate, DSA electrode (surface-area 50cm
2) be anode material, the sodium sulfate of 1000mg/L is ionogen, and interelectrode distance is 7cm, and electrolysis time is 60 ~ 120min minute, current density: 60mAcm
-2, at the temperature of 40 DEG C, use the oxybenzene compound aqueous solution that the present embodiment gained three-diemsnional electrode filler degraded concentration is 2500mg/L, under the condition of pH=8, electrolysis time is 100min, and phenol degrading rate is 85%.By reacting liquid filtering, washing and recycling three-diemsnional electrode filler, again with above-mentioned electrolytic condition electrolytic reaction 100min, phenol degrading rate is 85%.Third time, when repeating this step, the degradation rate of phenol was 81%.
The present invention has passed through on iron filings electroplating surface stable nickel coating, substantially prolongs the work-ing life of iron carbon filler.Fig. 1 is to the degradation rate time history plot of wastewater containing phenol according to three-diemsnional electrode filler of the present invention and conventional iron carbon filler.As shown in the figure, after adopting three-diemsnional electrode filler process wastewater containing phenol 200min of the present invention, the degradation rate of phenol can be made to reach more than 80%, far above 50% of conventional iron carbon filler.The three-diemsnional electrode filler of recycling higher than 70% to the degradation rate of wastewater containing phenol, still can realize the degradation rate higher than 60%, effectively improve the utilization ratio of iron carbon filler, reduce the cost of wastewater treatment after repeatedly Reusability.
The above embodiment only have expressed embodiments of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (6)
1. a three-diemsnional electrode filler, is characterized in that, component and each constituent mass per-cent of described three-diemsnional electrode filler are as follows: improvement iron filings 10%-25%, gac 35%-50% and mixing clay 30%-45%; And
Described mixing clay is that the kaolin of 85%-95% and the wilkinite of 5%-15% form by mass percent.
2. three-diemsnional electrode filler according to claim 1, is characterized in that, described three-diemsnional electrode filler is made up of the component that mass percent is following: improvement iron filings 25%, gac 37.5% and mixing clay 37.5%; And
Described mixing clay is that the kaolin of 90% and the wilkinite of 10% form by mass percent.
3. three-diemsnional electrode filler according to claim 1, is characterized in that, described three-diemsnional electrode filler is made up of the component that mass percent is following: improvement iron filings 15%, gac 45% and mixing clay 40%; And
Described mixing clay is that the kaolin of 89% and the wilkinite of 11% form by mass percent.
4. three-diemsnional electrode filler according to claim 1, is characterized in that, described three-diemsnional electrode filler is made up of the component that mass percent is following: improvement iron filings 22%, gac 44% and mixing clay 34%; And
Described mixing clay is that the kaolin of 91% and the wilkinite of 9% form by mass percent.
5. prepare a method for three-diemsnional electrode filler, it is characterized in that, comprise the following steps:
Step one: preparation improvement iron filings, its concrete steps comprise:
The iron filings of 0.5-2mm are put into the sodium hydroxide solution of 5%-15% by oil removing, and heating at 50 DEG C-80 DEG C is also filtered after supersound process 40min-100min;
Rust cleaning, will filter after dilute sulphuric acid that gained iron filings are placed in 5%-20% soaks 10-30min and filter through oil removal treatment;
Copper facing, will filter the copper-bath that gained iron filings are placed in 3%-7%, reacting by heating 60min at 40-60 DEG C through processing of rust removing, filters, dry, roasting 4 hours under starvation at 500 DEG C; And
Nickel plating, will be soaked in nickel-plating liquid through copper plating treatment gained iron filings, heat 40 ~ 60 DEG C of process 40min, filter under ultrasound condition, with distilled water wash 3 times, dry, and at 600 DEG C-800 DEG C, isolated air roasting 4 hours, obtains improveing iron filings;
Step 2: by described improvement iron filings, gac and the mass percent Homogeneous phase mixing mixing clay 10%-25%, 35%-50% and 30%-45%, add water in the mixture, shaken the particulate state making diameter 3-5mm;
Step 3: by described granular iron carbon filler 60 DEG C of vacuum dryings, put into retort furnace, add thermal bake-out 2-4 hour under the condition of isolating oxygen, obtained specific surface area is 0.4-1.0m
2the three-diemsnional electrode filler of/g.
6. method according to claim 5, is characterized in that, the preparation of described nickel-plating liquid comprises the following steps:
Step one: the nickel sulfate solution of the 3%-6% of preparation 500ml, adds Trisodium Citrate 20 ~ 35g, trolamine 10 ~ 15g successively;
Step 2: add 25 ~ 45g sodium hypophosphite solid under agitation, stirring and dissolving;
Step 3: being under agitation adjusted to pH with 10% sodium hydroxide solution is 8; And
Step 4: filter, obtain described nickel-plating liquid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1110160A (en) * | 1997-06-20 | 1999-01-19 | Nec Corp | Method for treating water by electrolytic oxidation |
| CN101817574A (en) * | 2010-04-16 | 2010-09-01 | 吉林大学 | Regular iron-carbon micro-electrolysis filler and preparation method thereof |
| CN102040263A (en) * | 2010-11-17 | 2011-05-04 | 北京航空航天大学 | Method for modifying micro-electrolytic fillers |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5365218A (en) * | 1976-11-25 | 1978-06-10 | Agency Of Ind Science & Technol | Electrolytic method for recovering silver from photographic spent solution |
| CN102001729A (en) * | 2009-09-03 | 2011-04-06 | 湖州四方格林自动化技术有限公司 | Electrolytic treatment method of heavy metal-containing wastewater |
| CN104556307B (en) * | 2013-10-09 | 2016-05-04 | 中国石油化工股份有限公司 | A kind of compound micro-electrolysis stuffing and preparation method thereof |
| CN103641207B (en) * | 2013-11-08 | 2015-12-02 | 华南理工大学 | A kind of Zinc-containing electroplating waste water combined electrolysis groove treatment process |
| CN105198048B (en) * | 2015-10-27 | 2018-01-02 | 雅本化学股份有限公司 | A kind of three-diemsnional electrode filler and preparation method thereof |
-
2015
- 2015-10-27 CN CN201510705791.2A patent/CN105198048B/en active Active
-
2016
- 2016-10-25 WO PCT/CN2016/103269 patent/WO2017071564A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1110160A (en) * | 1997-06-20 | 1999-01-19 | Nec Corp | Method for treating water by electrolytic oxidation |
| CN101817574A (en) * | 2010-04-16 | 2010-09-01 | 吉林大学 | Regular iron-carbon micro-electrolysis filler and preparation method thereof |
| CN102040263A (en) * | 2010-11-17 | 2011-05-04 | 北京航空航天大学 | Method for modifying micro-electrolytic fillers |
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