CN107930618A - Mn GAC particles and its application in 4 Chlorophenol of three-dimensional electrochemical reaction treatment - Google Patents
Mn GAC particles and its application in 4 Chlorophenol of three-dimensional electrochemical reaction treatment Download PDFInfo
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- CN107930618A CN107930618A CN201711132131.5A CN201711132131A CN107930618A CN 107930618 A CN107930618 A CN 107930618A CN 201711132131 A CN201711132131 A CN 201711132131A CN 107930618 A CN107930618 A CN 107930618A
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- chlorophenols
- gac
- electrochemical reaction
- gac particles
- dimensional electrochemical
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- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000002245 particle Substances 0.000 title claims abstract description 89
- 238000003487 electrochemical reaction Methods 0.000 title claims abstract description 57
- 238000011282 treatment Methods 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000008187 granular material Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 10
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000001802 infusion Methods 0.000 claims abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 39
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 26
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 25
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000460 chlorine Substances 0.000 claims description 22
- 229910052801 chlorine Inorganic materials 0.000 claims description 22
- 239000002351 wastewater Substances 0.000 claims description 21
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 14
- 239000013067 intermediate product Substances 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- -1 hydroxyl free radical Chemical class 0.000 claims description 9
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000009514 concussion Effects 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- 239000007832 Na2SO4 Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 230000007423 decrease Effects 0.000 claims 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 15
- 238000011068 loading method Methods 0.000 abstract description 2
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 abstract 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 238000006731 degradation reaction Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 12
- 239000001530 fumaric acid Substances 0.000 description 12
- 239000011572 manganese Substances 0.000 description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 5
- 238000004811 liquid chromatography Methods 0.000 description 5
- 238000004088 simulation Methods 0.000 description 5
- 206010010254 Concussion Diseases 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- XXWYUBYMBOTAGQ-UHFFFAOYSA-N 6-diazo-4,5-dinitrocyclohexa-2,4-dien-1-ol Chemical compound OC1C=CC([N+]([O-])=O)=C([N+]([O-])=O)C1=[N+]=[N-] XXWYUBYMBOTAGQ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 238000010525 oxidative degradation reaction Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000006652 catabolic pathway Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000013178 mathematical model Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011369 optimal treatment Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- KSSNXJHPEFVKHY-UHFFFAOYSA-N phenol;hydrate Chemical compound O.OC1=CC=CC=C1 KSSNXJHPEFVKHY-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910006654 β-PbO2 Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- C02F1/467—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
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The present invention discloses Mn GAC particles, which is the support type Mn GAC particles that Mn metal ions are prepared using infusion process by loading modification granular activated carbon.Using support type Mn 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 Mn GAC particles, the removal rate of 4 chlorophenols can reach more than 99%.Meanwhile particle preparation process is simple, particle may be reused, and greatly reduce the processing cost of 4 Chlorophenols, and improve 4 Chlorophenol treatment effeciencies.
Description
Technical field
The invention belongs to technical field of sewage, more particularly to Mn-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 Mn-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
Mn-GAC particles, the particle are to be prepared into Mn metal ions by loading modification granular activated carbon using infusion process
The support type Mn-GAC particles arrived.
Further as technical solution is improved, above-described Mn-GAC particles, the support type Mn-GAC particles
Preparation method specific steps include：First by Mn (NO3)2It is dissolved in organic alcohol solvent and obtains mixed solution, then GAC is immersed in
In mixed solution, shaking table 150-200r/min concussion 2 it is small when more than, obtain support type Mn-GAC particle crude products, then drying,
200-300 DEG C of roasting can obtain support type Mn-GAC particles.
Further as technical solution is improved, in above-described Mn-GAC particles preparation method, shaking table frequency
Rate is 150-200r/min, and the calcination temperature is 200-300 DEG C.
Further as technical solution is improved, above-described Mn-GAC particles, Mn (NO3)2Mass ratio with GAC is：
1:10~1:20.
Further as technical solution is improved, and above-described Mn-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 Mn-GAC particles preparation method, the drying temperature
Spend for 100-110 DEG C.
Application of the Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols described in any of the above, with load
Type Mn-GAC particles are granule electrode, and using shape steady electrode (DSA) electrode as anode, using titanium plate as cathode, structure bipolar type is three-dimensional
Electrochemical reactor, three-dimensional electrochemical reaction is carried out under electrochemical oxidation process, 4- chlorophenols are finally degraded to carbon dioxide
And water.
Further as technical solution is improved, and above-described Mn-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 Mn-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 Mn-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 Mn-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 Mn-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 99% in the 4- Chlorophenols.
The invention has the advantages that：
The present invention is constructed three-dimensional electrochemical reactor using Mn-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.MnO at the same time2It is the n-type semiconductor of oxygen-starved, conductivity is high, and corrosion resistance is strong, using particle
Activated carbon as carrier it is relatively low compared to other carriers its prices, derive from a wealth of sources.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, substantially increases the removal rate of 4- chlorophenols.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of Mn-GAC particles.
Fig. 2 schemes for Mn-GAC particle surface elemental analyses EDS.
Fig. 3 is Mn-GAC granule electrode XRD diagram
Fig. 4 is the analysis oxygen polarization curve of Mn-GAC granule electrodes
Fig. 5 is the cyclic voltammetry curve figure of Mn-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
Mn-GAC particles prepare embodiment 1
(1) granular activated carbon pre-processes：Granular activated carbon is boiled to clean, drying with a large amount of deionized waters, it is spare.
(2) press or mass ratio is：1:10.Mn (NO are weighed successively3)2And GAC.
(3) first by Mn (NO3)2It is dissolved in organic alcohol solvent and obtains mixed solution, then GAC is immersed in mixed solution,
When shaking table 150r/min concussions 2 are small, support type Mn-GAC particle crude products are obtained, then drying, 200 DEG C of roastings can be loaded
Type Mn-GAC particles.
Mn-GAC particles prepare embodiment 2
(1) granular activated carbon pre-processes：Granular activated carbon is boiled to clean, drying with a large amount of deionized waters, it is spare.
(2) press or mass ratio is：1:15.Mn (NO are weighed successively3)2And GAC.
(3) first by Mn (NO3)2It is dissolved in organic alcohol solvent and obtains mixed solution, then GAC is immersed in mixed solution,
When shaking table 175r/min concussions 4 are small, support type Mn-GAC particle crude products are obtained, then drying, 250 DEG C of roastings can be loaded
Type Mn-GAC particles.
Mn-GAC particles prepare embodiment 3
(1) granular activated carbon pre-processes：Granular activated carbon is boiled to clean, drying with a large amount of deionized waters, it is spare.
(2) press or mass ratio is：1:20.Mn (NO are weighed successively3)2And GAC.
(3) first by Mn (NO3)2It is dissolved in organic alcohol solvent and obtains mixed solution, then GAC is immersed in mixed solution,
When shaking table 200r/min concussions 6 are small, support type Mn-GAC particle crude products are obtained, then drying, 300 DEG C of roastings can be loaded
Type Mn-GAC particles.
The physicochemical property of support type Mn-GAC particles prepared by embodiment 1 determines
Granule electrode surface topography and structural analysis：
(1) scanning electron microscope analysis
Using field emission scanning electron microscope (SUPRA 55Sapphire, German Carl Zeiss Inc.) to activated carbon table
Face pattern is analyzed, using the OXFORD X-MaxN51-XMX1004 energy disperse spectroscopies of scanning electron microscope configuration to modification activities charcoal
On element composition analyzed.
(2) X-ray diffraction analysis
Activated carbon is divided using X-ray diffractometer (X ' Pert PRO, Dutch Panaco company PANalytical)
Analysis, test condition are：Copper target0.026 ° of step-length, 5 ° -80 ° of scanning range, often walks the residence time
20.4s, voltage 40V, electric current 40mA.
Granule electrode electrochemical property test：
Support type granule electrode electrochemical property test mainly provides theoretical foundation, electrochemistry for electro oxidation mechanism
Performance generally selects three-electrode system to be tested.This research is using occasion China CHI660E electrochemical workstations to granule electrode
Chemical property is tested, and using homemade carbon paste electrode as working electrode, saturated calomel electrode is as reference electrode, platinum electrode
Tested for auxiliary electrode.The production method of carbon paste electrode is：Appropriate granule electrode grind into powder is taken, with granule electrode：
Conductive black=8:1 amount adds a certain amount of conductive black, and liquid stone is added after granule electrode powder and conductive black are mixed
It is waxed into paste, inserted in carbon paste electrode.In the range of 1-1.5V, speed is swept respectively in 0.15mol/LNa with 20mV/s2SO4
And 0.15mol/LNa2SO4In+0.5g/L4- chlorophenol solution, its linear volt-ampere working curve and cyclic voltammetry curve is measured.
Through measuring：
The scanning electron microscope (SEM) photographs of Mn-GAC particles is as shown in Figure 1, Fig. 1 shows that the grain diameter on Mn-GAC surfaces is smaller, activity
The tiny size of carbon surface particle is homogeneous, and preferably, as three-diemsnional electrode when can be effectively increased the specific surface area of granule electrode to dispersiveness,
It is favourable to improving electro-oxidation reaction efficiency so as to add the contact area of granule electrode surface and organic pollution.
Mn-GAC particle surface elemental analyses EDS is schemed as shown in Fig. 2, Fig. 2 shows successfully to have loaded corresponding Mn on GAC
Metal oxide.
Sb-GAC granule electrodes XRD diagram is as shown in figure 3, Fig. 3 shows not find Mn element obvious characteristic diffraction maximums, but energy
Spectrum analysis detects the presence of manganese element, show Sb-GAC loads containing Mn oxide, into unformed armorphous fractions distribution
In GAC surfaces.
The analysis oxygen polarization curve of Mn-GAC granule electrodes is as shown in figure 4, Fig. 4 shows Mn-GAC granule electrodes in Xi Yang areas
Electric current is between 1.4V-1.6V.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 Mn-GAC granule electrodes is as shown in figure 5, Fig. 5 shows that Mn-GAC occurs 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 Mn-GAC particles carry out and embodiment
The identical detection of the 1 support type Mn-GAC particles prepared, load of the result that all embodiments detect with applying the preparation of example 1
The corresponding every detection of type Mn-GAC particles is identical, and illustrates that prepared product reappearance is fabulous.
Application Example 1 of the Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：Prepared and implemented with Mn-GAC particles
Support type Mn-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 99.2% in the present embodiment 4- Chlorophenols.
Application Example 2 of the Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：Prepared and implemented with Mn-GAC particles
Support type Mn-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 more than 99.1% in the present embodiment 4- Chlorophenols.
Application Example 3 of the Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：Prepared and implemented with Mn-GAC particles
Support type Mn-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 1.5A, particle
Electrode dosage 15g.Three-dimensional electrochemical reaction is carried out under electrochemical oxidation process, the temperature of three-dimensional electrochemical reaction is taken the photograph for 50
4- chlorophenols, are first degraded to the intermediate product of hydroxyl free radical, are finally degraded to carbon dioxide and water by family name's 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 99.5% in the present embodiment 4- Chlorophenols.
Application Example 4 of the Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：Prepared and implemented with Mn-GAC particles
Support type Mn-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 3.5cm, kinetic current 1.75A, grain
Sub-electrode dosage 18g.Three-dimensional electrochemical reaction is carried out under electrochemical oxidation process, the temperature of three-dimensional electrochemical reaction is 55
Degree 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 99.6% in the present embodiment 4- Chlorophenols.
Application Example 5 of the Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols
Application of the Mn-GAC particles in three-dimensional electrochemical reaction treatment 4- Chlorophenols：Prepared and implemented with Mn-GAC particles
Support type Mn-GAC particles prepared by example 2 are granule electrode, using dimensional stable anode DSA electrodes as anode, using titanium plate as cathode, with
Na2SO is electrolyte, builds bipolar type three-dimensional electrochemical reactor, and 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 more than 99.6% in the present embodiment 4- Chlorophenols.
Claims (10)
1.Mn-GAC particles, it is characterised in that：The Mn-GAC particles are that Mn metal ions are passed through load using infusion process
The support type Mn-GAC particles that modification granular activated carbon is prepared.
2. Mn-GAC particles according to claim 1, it is characterised in that：The support type Mn-GAC particle preparation methods
Specific steps include：First by Mn (NO3)2It is dissolved in organic alcohol solvent and obtains mixed solution, then GAC is immersed in mixed solution
In, shaking table 150-200r/min concussion 2 it is small when more than, obtain support type Mn-GAC particle crude products, then drying, 200-300 DEG C
Roasting can obtain support type Mn-GAC particles.
3. Mn-GAC particles according to claim 1 or 2, it is characterised in that：Mn(NO3)2Mass ratio with GAC is：1:10
~1:20.
4. Mn-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 Mn-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 Mn-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 Mn-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 Mn-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 Mn-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 Mn-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 Mn-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 99% in the 4- Chlorophenols.
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| CN113716657A (en) * | 2021-09-22 | 2021-11-30 | 北京林业大学 | Preparation method and application of green recyclable metal oxide embedded ordered mesoporous carbon particle electrode |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6692632B1 (en) * | 1999-09-01 | 2004-02-17 | University Of Abertay Dundee | Method of producing hydroxyl radicals for chemical reactions |
| JP2014161786A (en) * | 2013-02-25 | 2014-09-08 | Nissan Motor Co Ltd | Catalyst particle and method for producing the same |
| CN106430456A (en) * | 2016-11-21 | 2017-02-22 | 北京益清源环保科技有限公司 | Modified activated carbon particle electrode with function using electro-catalysis to remove chlorophenol and preparation method |
-
2017
- 2017-11-15 CN CN201711132131.5A patent/CN107930618A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6692632B1 (en) * | 1999-09-01 | 2004-02-17 | University Of Abertay Dundee | Method of producing hydroxyl radicals for chemical reactions |
| JP2014161786A (en) * | 2013-02-25 | 2014-09-08 | Nissan Motor Co Ltd | Catalyst particle and method for producing the same |
| CN106430456A (en) * | 2016-11-21 | 2017-02-22 | 北京益清源环保科技有限公司 | Modified activated carbon particle electrode with function using electro-catalysis to remove chlorophenol and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 孔令国等: "负载型三维粒子电极降解甲基橙模拟废水研究", 《中国环境科学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113716657A (en) * | 2021-09-22 | 2021-11-30 | 北京林业大学 | Preparation method and application of green recyclable metal oxide embedded ordered mesoporous carbon particle electrode |
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