CN107335435A - A kind of electric fenton catalyst, negative electrode and sewage water treatment method - Google Patents
A kind of electric fenton catalyst, negative electrode and sewage water treatment method Download PDFInfo
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- CN107335435A CN107335435A CN201710648455.8A CN201710648455A CN107335435A CN 107335435 A CN107335435 A CN 107335435A CN 201710648455 A CN201710648455 A CN 201710648455A CN 107335435 A CN107335435 A CN 107335435A
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- Prior art keywords
- catalyst
- electric fenton
- electrode
- fenton catalyst
- sewage
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 239000010865 sewage Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 19
- 239000010802 sludge Substances 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000005336 cracking Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000006166 lysate Substances 0.000 claims abstract description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 13
- 230000001681 protective effect Effects 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 16
- 239000003344 environmental pollutant Substances 0.000 claims description 4
- 231100000719 pollutant Toxicity 0.000 claims description 4
- 229920000557 Nafion® Polymers 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 16
- 239000007789 gas Substances 0.000 abstract description 12
- 229910052742 iron Inorganic materials 0.000 abstract description 9
- 230000033558 biomineral tissue development Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005844 autocatalytic reaction Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000012958 reprocessing Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 239000000701 coagulant Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 4
- -1 iron ion Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010841 municipal wastewater Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 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 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/28—Per-compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/46125—Electrical variables
- C02F2201/46135—Voltage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4619—Supplying gas to the electrolyte
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of electric fenton catalyst, is made according to following steps：A the sludge drying of molysite) is will be enriched in, obtains presoma；B) presoma is heated to cracking under protective gas atmosphere, obtain lysate；C after) lysate is immersed cleaning in acid solution, dried, electric fenton catalyst is obtained.The present invention handles to obtain efficient electric Fenton cathod catalyst by the way that caused sludged waste material during municipal sewage treatment is carried out into reprocessing, can add iron ion and H without external source2O2Under conditions of, the iron ion that is carried by catalyst itself, with electrode autocatalysis reduction oxygen caused by H2O2Reaction produces OH free radicals, carrys out efficient mineralization degradable organic pollutant, realizes the recycling of sludge.Present invention also offers a kind of negative electrode and the method for sewage disposal.
Description
Technical field
At urban sewage treatment technology field, more particularly to a kind of electric fenton catalyst, negative electrode and sewage
Reason method.
Background technology
In recent years, with the continuous quickening of Urbanization in China and the continuous rising of the level of urbanization, urban water pollution
Problem is also increasingly serious.According to China Statistical Yearbook (2016 editions) statistics, China's waste water in 2015 produces total amount and reached
To 735 billion cubic meters, it brings huge burden and pressure to urban environmental hygiene.Therefore, how municipal wastewater is realized
High-efficiency and economic processing is just particularly important.In the processing procedure of municipal wastewater, the characteristics of iron-based coagulant is because of Cheap highly effective,
It uses very extensive.But the substantial amounts of chemical sludge for being rich in molysite at the same time, is also generated, how appropriate must handle disposal
This kind of chemical sludge is to ensure the very important content of urban water environmental quality.
Municipal sludge rich in molysite can be used as H2O2The source of iron of activation, and then it is used for for example electric Fenton of advanced oxidation processes
Method is made a return journey except the persistent organic pollutants in water body.But due to H2O2Preparation cost it is higher and its storage transport etc. exist
Certain security risk, if H can be realized2O2Fabricated in situ and using then can undoubtedly greatly reducing processing cost and environment
Risk.Therefore, if the efficient catalytic of synthesizing new using the sludge rich in molysite as raw material, can be regulated and controled by certain means
Agent, fabricated in situ H2O2While in-situ activation H again2O2, realize that the mineralising of pollutant removes, then can not only substantially reduce advanced
The operating cost of oxidation technology, new changing rejected material to useful resource can also be realized.
The content of the invention
It is an object of the invention to provide a kind of electric fenton catalyst, negative electrode and sewage water treatment method, the electricity in the present invention
Fenton catalyst energy consumption is low, H2O2Yield is high, mineralization of organic material removal effect is good, realizes the recycling of sludge.
The present invention provides a kind of electric fenton catalyst, is made according to following steps：
A the sludge drying of molysite) is will be enriched in, obtains presoma；
B) presoma is heated to cracking under protective gas atmosphere, obtain lysate；
C after) lysate is immersed cleaning in acid solution, dried, electric fenton catalyst is obtained.
Preferably, the temperature of the drying is 90~120 DEG C.
Preferably, the protective gas includes NH3、N2Or Ar.
Preferably, the temperature of the cracking is 600~800 DEG C；
The time of the cracking is 2~6 hours.
Preferably, the acid solution is preferably HCl solution, HF solution or HClO4Solution；
The mass concentration of the acid solution is 5~20%.
This distribution provides a kind of negative electrode, including conductive substrates and the catalyst that is supported in conductive substrates；
The catalyst is electric fenton catalyst described above.
Preferably, the catalyst is loaded in conductive substrates by following steps：
The Nafion solution that catalyst, the alcoholic solution of volume fraction 50~100% and volume fraction are 1~5% is mixed,
Obtained mixed solution coating and conductive substrates surface, negative electrode is obtained after drying.
The present invention provides a kind of sewage water treatment method, comprises the following steps：
Sewage is inserted in working electrode, to electrode and reference electrode, applies current potential, and the drum in sewage on the working electrode (s
Enter air, the pollutant in sewage of degrading；
The working electrode is negative electrode above.
Preferably, the current potential of the application is 0.25~0.45V.
Preferably, the air-blowing amount of the air is 50~500m3/(m3Water h).
The present invention provides a kind of electric fenton catalyst, is made according to following steps：A the sludge drying of molysite) is will be enriched in, is obtained
To presoma；B) presoma is heated to cracking under protective gas atmosphere, obtain lysate；C lysate) is immersed into acid solution
Middle cleaning, after drying, obtain electric fenton catalyst.
The present invention handles to obtain efficiently by the way that caused sludged waste material during municipal sewage treatment is carried out into reprocessing
Electric Fenton cathod catalyst, iron ion and H can added without external source2O2Under conditions of, carried by catalyst itself
Iron ion, H caused by oxygen is reduced with electrode autocatalysis2O2Reaction produces OH free radicals, carrys out the organic dirt of efficient mineralization degraded
Thing is contaminated, realizes the recycling of sludge.Compared with prior art, using the invention has the advantages that：
1st, raw material are solid waste, very big to reduce cost；
2nd, the elctro-catalyst O obtained2The selectivity and H of reduction2O2Yield is high；
3rd, the electrode of catalyst is loaded with, operating point position is low, reduce further the processing energy consumption of system；
4th, H is added without external source2O2Activator, it is very big to save operating cost.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is the preparation flow figure of electric fenton catalyst in the present invention.
Embodiment
The present invention provides a kind of electric fenton catalyst, is made according to following steps：
A the sludge drying of molysite) is will be enriched in, obtains presoma；
B) presoma is heated to cracking under protective gas atmosphere, obtain lysate；
C after) lysate is immersed cleaning in acid solution, dried, electric fenton catalyst is obtained.
For the preparation flow of the electric fenton catalyst of the present invention referring to Fig. 1, Fig. 1 is the preparation of electric fenton catalyst in the present invention
Flow chart.
The present invention adds iron salt coagulant and handled preferably by after municipal sewage collection system, obtains the sludge rich in molysite.
The present invention does not have special limitation to the source of the municipal sewage, the iron salt coagulant be preferably iron chloride,
One or more in frerrous chloride, poly-ferric chloride；The iron salt coagulant add concentration be preferably 10~50mg/L (with
Fe is counted).The obtained sludge rich in molysite is rich in iron and organic matter.The present invention is to the processing method of the municipal sewage without spy
Different limitation, the processing method commonly used using those skilled in the art.
After obtaining the sludge rich in molysite, the present invention is baked to, and obtains presoma, the temperature of the drying is preferably 90
~120 DEG C, more preferably 100~110 DEG C, most preferably 105 DEG C, the present invention do not have special limit to the time of the drying
System, the moisture removal in the sludge is complete.
After obtaining presoma, it is carried out Pintsch process by the present invention under protective gas atmosphere, obtains lysate.At this
In invention, the protective gas is preferably NH3、N2Or Ar, more preferably NH3Or Ar, most preferably NH3；The protectiveness gas
The flow of body is preferably 10~40mL/min, more preferably 20~30mL/min.The temperature of the cracking is preferably 600~800
℃；The time of the cracking is preferably 2~6 hours, and the present invention realizes the cracking temperature by temperature programming, the heating
Speed is preferably 1~10 DEG C/min, more preferably 3~8 DEG C/min, most preferably 5~6 DEG C/min.In the cracking bar of the present invention
The pyrolysis product for cracking to obtain under part is cracking carbon.
After obtaining lysate, the present invention is dipped in acid solution and cleaned, and removes ash and grades impurity, is obtained after drying
Electric fenton catalyst.In the present invention, the acid solution is preferably HCl solution, HF solution or HClO4Solution；The acid solution
Mass concentration be preferably 5~20%, more preferably 10~15%；Present invention preferably employs acid solution clean 2~3 times, then
Presented again with distilled water flushing to pH value neutral.The drying is preferably to dry, and the temperature of the drying is preferably 90~120
DEG C, more preferably 100~110 DEG C, most preferably 105 DEG C are complete by the moisture drying in the pyrolysis product.
Present invention also offers a kind of negative electrode, including conductive substrates and the catalyst being supported in the conductive substrates, institute
Catalyst is stated as electric fenton catalyst above.The present invention preferably by the catalyst be scattered in volume fraction for 50~
In 100% alcoholic solution, then add volume fraction be 1~5% Nafion solution to strengthen electric conductivity, obtained mixing is molten
Liquid is coated in the surface of conductive substrates, and negative electrode is obtained after drying.
In the present invention, the mass concentration of the catalyst in the solution is 10~20g/L；The conductive substrates are preferably
Carbon paper substrate, the temperature of the drying is preferably 30~60 DEG C, more preferably 40~50 DEG C.
Present invention also offers a kind of method of sewage disposal, comprise the following steps：
Sewage is inserted in working electrode, to electrode and reference electrode, applies current potential, and the drum in sewage on the working electrode (s
Enter air, the pollutant in sewage of degrading.
In the present invention, the working electrode is negative electrode described above, and the reference electrode is not particularly limited, can be with
It is Ag/AgCl；It is described there is no special limitation to electrode, can be platinum electrode.The present invention comes to the pending sewage
Source does not have special limitation, such as sewage containing phenol, can be waste water from dyestuff specifically, can be chemical sewage, such as contains Luo Dan
Bright B waste water；Can be agricultural chemicals waste water, such as waste water containing Atrazine.
In the present invention, the current potential applied on the working electrode is preferably 0.25~0.45V (relative to reversible hydrogen electricity
Pole RHE), preferably 0.35~0.4V；The air-blowing amount of the air is preferably 50~500m3/(m3Water h), more preferably 100
~400m3/(m3Water h), most preferably 200~300m3/(m3Water h).
The present invention provides a kind of electric fenton catalyst, is made according to following steps：A the sludge drying of molysite) is will be enriched in, is obtained
To presoma；B) presoma is heated to cracking under protective gas atmosphere, obtain lysate；C lysate) is immersed into acid solution
Middle cleaning, after drying, obtain electric fenton catalyst.
The present invention handles to obtain efficiently by the way that caused sludged waste material during municipal sewage treatment is carried out into reprocessing
Electric Fenton cathod catalyst, iron ion and H can added without external source2O2Under conditions of, carried by catalyst itself
Iron ion, H caused by oxygen is reduced with electrode autocatalysis2O2Reaction produces OH free radicals, carrys out the organic dirt of efficient mineralization degraded
Thing is contaminated, realizes the recycling of sludge.Compared with prior art, using the invention has the advantages that：
1st, raw material are solid waste, very big to reduce cost；
2nd, the elctro-catalyst O obtained2The selectivity and H of reduction2O2Yield is high；
3rd, the electrode of catalyst is loaded with, operating point position is low, reduce further the processing energy consumption of system；
4th, H is added without external source2O2Activator, it is very big to save operating cost.
In order to further illustrate the present invention, with reference to embodiments to a kind of electric fenton catalyst provided by the invention, the moon
Pole and sewage water treatment method are described in detail, but can not be understood as limiting the scope of the present invention.
Embodiment 1
Take 20L municipal sewage plants to intake, iron chloride is added to above-mentioned according to 30mg/L (with Fe ionometers) concentration
In sewage, 20min quickly is stirred under 30rpm again after stirring 2min at 200 rpm, filtering acquisition is aqueous after staticly settling
Sludge, the sludge is dried under the conditions of 105 DEG C and goes moisture removal to obtain presoma.
The above-mentioned presoma acquired is placed in porcelain boat and is put into tube furnace, is passed through NH in advance3Gas is to catch up with blowpipe
Air.Then temperature programming is set to 800 DEG C and to maintain 6h according to 5 DEG C/min heating rate.Treat that tube furnace is down to normal temperature
The carbon that cracking obtains is removed afterwards, is cleaned repeatedly after 3 times with 10%HCl solution and neutrality is presented with distilled water flushing to pH again, will be clear
Material after washing obtains catalyst after 105 DEG C of drying again.
10mg catalyst is taken into 0.5mL75% aqueous isopropanols, adds ultrasonic disperse after 10 μ LNafion solution
30min, the uniform suspension after disperseing must be covered in 3 × 3cm carbon paper substrate, are dried under the conditions of 50 DEG C and are obtained electricity
Pole.
The application of catalyst：Using above-mentioned electrode as working electrode, platinum filament is that Ag/AgCl is reference electrode structure to electrode
Electro-chemical systems are built, using 50mg/L phenol as process object.Insert electrodes into 50mL phenol solutions, apply 0.25V (vs
RHE) operating potential, 200m is continuously blasted3/m3/ h air.Catalyst H2O2Average yield can reach 12.7mmol/h/g,
Phenol can be removed completely in 40min, and TOC clearances can reach more than 60% in 4h.
Embodiment 2
Take 20L municipal sewage plants to intake, iron chloride is added to above-mentioned according to 30mg/L (with Fe ionometers) concentration
In sewage, 20min quickly is stirred under 30rpm again after stirring 2min at 200 rpm, filtering acquisition is aqueous after staticly settling
Sludge, the sludge is dried under the conditions of 105 DEG C and goes moisture removal to obtain presoma.
The above-mentioned presoma acquired is placed in porcelain boat and is put into tube furnace, is passed through Ar gas in advance to catch up with blowpipe
Air.Then temperature programming is set to 600 DEG C and to maintain 6h according to 5 DEG C/min heating rate.After tube furnace is down to normal temperature
The carbon that cracking obtains is removed, is cleaned repeatedly after 3 times with 10%HCl solution and neutrality is presented with distilled water flushing to pH again, will cleaned
Later material obtains catalyst after 105 DEG C of drying again.
10mg catalyst is taken into the aqueous isopropanols of 0.5mL 75%, adds ultrasonic disperse after 10 μ LNafion solution
30min, the uniform suspension after disperseing must be covered in 3 × 3cm carbon paper substrate, are dried under the conditions of 50 DEG C and are obtained electricity
Pole.
The application of catalyst：Using above-mentioned electrode as working electrode, platinum filament is that Ag/AgCl is reference electrode structure to electrode
Electro-chemical systems are built, are process object with 50mg/L waste water from dyestuff (rhodamine B).Insert electrodes into the above-mentioned waste water of 50mL,
Apply 0.25V (vs RHE) operating potential, continuously blast 200m3/m3/ h air.Catalyst H2O2Average yield can reach
10mmol/h/g, rhodamine B can be removed completely in 30min, and TOC clearances can reach more than 65% in 4h.
Embodiment 3
Take 20L municipal sewage plants to intake, iron chloride is added to above-mentioned according to 30mg/L (with Fe ionometers) concentration
In sewage, 20min quickly is stirred under 30rpm again after stirring 2min at 200 rpm, filtering acquisition is aqueous after staticly settling
Sludge, the sludge is dried under the conditions of 105 DEG C and goes moisture removal to obtain presoma.
The above-mentioned presoma acquired is placed in porcelain boat and is put into tube furnace, is passed through NH in advance3Gas is to catch up with blowpipe
Air.Then temperature programming is set to 800 DEG C and to maintain 6h according to 5 DEG C/min heating rate.Treat that tube furnace is down to normal temperature
The carbon that cracking obtains is removed afterwards, is cleaned repeatedly after 3 times with 10%HCl solution and neutrality is presented with distilled water flushing to pH again, will be clear
Material after washing obtains catalyst after 105 DEG C of drying again.
10mg catalyst is taken into 0.5mL75% aqueous isopropanols, adds ultrasonic disperse after 10 μ LNafion solution
30min, the uniform suspension after disperseing must be covered in 3 × 3cm carbon paper substrate, are dried under the conditions of 50 DEG C and are obtained electricity
Pole.
The application of catalyst：Using above-mentioned electrode as working electrode, platinum filament is that Ag/AgCl is reference electrode structure to electrode
Electro-chemical systems are built, using 50mg/L agricultural chemicals (Atrazine) waste water as process object.Insert electrodes into 50mL agricultural chemicals waste waters,
Apply 0.35V (vs RHE) operating potential, continuously blast 400m3/m3/ h air.Catalyst H2O2Average yield can reach
13mmol/h/g, Atrazine can be removed completely in 30min, and TOC clearances can reach more than 55% in 4h.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of electric fenton catalyst, is made according to following steps：
A the sludge drying of molysite) is will be enriched in, obtains presoma；
B) presoma is heated to cracking under protective gas atmosphere, obtain lysate；
C after) lysate is immersed cleaning in acid solution, dried, electric fenton catalyst is obtained.
2. electric fenton catalyst according to claim 1, it is characterised in that the temperature of the drying is 90~120 DEG C.
3. electric fenton catalyst according to claim 1, it is characterised in that the protective gas includes NH3、N2Or Ar.
4. electric fenton catalyst according to claim 1, it is characterised in that the temperature of the cracking is 600~800 DEG C；
The time of the cracking is 2~6 hours.
5. electric fenton catalyst according to claim 1, it is characterised in that the acid solution is preferably HCl solution, HF molten
Liquid or HClO4Solution；
The mass concentration of the acid solution is 5~20%.
6. a kind of negative electrode, including conductive substrates and the catalyst that is supported in conductive substrates；
The catalyst is the electric fenton catalyst described in Claims 1 to 5 any one.
7. negative electrode according to claim 6, it is characterised in that the catalyst loads to conductive substrates by following steps
On：
The Nafion solution that catalyst, the alcoholic solution of volume fraction 50~100% and volume fraction are 1~5% is mixed, obtained
Mixed solution coating with conductive substrates surface, obtain negative electrode after drying.
8. a kind of sewage water treatment method, comprises the following steps：
Sewage is inserted in working electrode, to electrode and reference electrode, applies current potential on the working electrode (s, and sky is blasted in sewage
Gas, degrade sewage in pollutant；
The working electrode is the negative electrode in claim 6 or 7.
9. sewage water treatment method according to claim 8, it is characterised in that the current potential of the application is 0.25~0.45V.
10. sewage water treatment method according to claim 8, it is characterised in that the air-blowing amount of the air is 50~500m3/
(m3Water h).
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| WO2020122326A1 (en) * | 2018-12-14 | 2020-06-18 | 한국과학기술연구원 | Catalyst for electro-fenton reacton system consisting of sulfated transition metal oxides, electrode comprising same, and electro-fenton reaction system using same |
| CN111533223A (en) * | 2020-05-12 | 2020-08-14 | 北京林业大学 | FeS2Cathode heterogeneous electro-Fenton water treatment method |
| CN112064084A (en) * | 2020-08-06 | 2020-12-11 | 陕西科技大学 | Preparation method of metal monoatomic titanium suboxide electrode |
| CN113526646A (en) * | 2021-08-20 | 2021-10-22 | 中南大学 | electro-Fenton system for in-situ production of hydrogen peroxide by cathode/anode and application of electro-Fenton system in strengthening degradation of organic pollutants |
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| WO2020122326A1 (en) * | 2018-12-14 | 2020-06-18 | 한국과학기술연구원 | Catalyst for electro-fenton reacton system consisting of sulfated transition metal oxides, electrode comprising same, and electro-fenton reaction system using same |
| CN109604624A (en) * | 2019-01-08 | 2019-04-12 | 哈尔滨工业大学 | A kind of method and application preparing nano zero valence iron using water treatment plant's iron containing sludge |
| CN110482656A (en) * | 2019-09-05 | 2019-11-22 | 中国科学院过程工程研究所 | A kind of resource utilization method of coagulation sludge and products thereof and purposes |
| CN111533223A (en) * | 2020-05-12 | 2020-08-14 | 北京林业大学 | FeS2Cathode heterogeneous electro-Fenton water treatment method |
| CN112064084A (en) * | 2020-08-06 | 2020-12-11 | 陕西科技大学 | Preparation method of metal monoatomic titanium suboxide electrode |
| CN112064084B (en) * | 2020-08-06 | 2022-10-25 | 陕西科技大学 | Preparation method of metal monoatomic titanium suboxide electrode |
| CN113526646A (en) * | 2021-08-20 | 2021-10-22 | 中南大学 | electro-Fenton system for in-situ production of hydrogen peroxide by cathode/anode and application of electro-Fenton system in strengthening degradation of organic pollutants |
| CN113526646B (en) * | 2021-08-20 | 2022-04-05 | 中南大学 | electro-Fenton system for in-situ production of hydrogen peroxide by cathode/anode and application of electro-Fenton system in strengthening degradation of organic pollutants |
| CN114392754A (en) * | 2022-02-07 | 2022-04-26 | 中国石油大学(北京) | Modified activated carbon fiber composite material, preparation method thereof, heterogeneous electro-Fenton catalytic composite material and application thereof |
| CN114392754B (en) * | 2022-02-07 | 2022-12-23 | 中国石油大学(北京) | Modified activated carbon fiber composite material, preparation method thereof, heterogeneous electro-Fenton catalytic composite material and application thereof |
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