CN107335435B - A kind of electricity fenton catalyst, cathode and sewage water treatment method - Google Patents
A kind of electricity fenton catalyst, cathode and sewage water treatment method Download PDFInfo
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- CN107335435B CN107335435B CN201710648455.8A CN201710648455A CN107335435B CN 107335435 B CN107335435 B CN 107335435B CN 201710648455 A CN201710648455 A CN 201710648455A CN 107335435 B CN107335435 B CN 107335435B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 239000010865 sewage Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 22
- 230000005611 electricity Effects 0.000 title description 7
- 238000001035 drying Methods 0.000 claims abstract description 29
- 239000010802 sludge Substances 0.000 claims abstract description 24
- 238000005336 cracking Methods 0.000 claims abstract description 18
- 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 7
- 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
- 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
- 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
- 150000003254 radicals Chemical class 0.000 abstract description 3
- 230000009467 reduction Effects 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
- 239000000243 solution Substances 0.000 description 28
- 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 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
- 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
- 238000012545 processing Methods 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process 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
- 239000003905 agrochemical Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 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
- 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 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
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution 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
- 239000000575 pesticide Substances 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 the following steps: A) the sludge drying that will be enriched in molysite, obtain presoma；B) presoma is heated under protective gas atmosphere to cracking, obtain lysate；C after lysate) is immersed cleaning in acid solution, drying, electric fenton catalyst is obtained.The present invention handles to obtain efficient electric Fenton cathod catalyst by the way that the sludged waste material generated during municipal sewage treatment is carried out reprocessing, can add iron ion and H without external source2O2Under conditions of, the iron ion being had by catalyst itself, the H generated with electrode autocatalysis reduction oxygen2O2Reaction generates OH free radical, carrys out efficient mineralization degradable organic pollutant, realizes the resource utilization of sludge.The present invention also provides a kind of methods of cathode and sewage treatment.
Description
Technical field
The invention belongs at urban sewage treatment technology field more particularly to a kind of electric fenton catalyst, cathode and sewage
Reason method.
Background technique
In recent years, with the continuous continuous rising accelerated with the level of urbanization of Urbanization in China, urban water pollution
Problem is also increasingly serious.According to China Statistical Yearbook (2016 editions) statistical data, China's waste water in 2015 generates total amount and has 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 treatment process of municipal wastewater, the characteristics of iron-based coagulant is because of Cheap highly effective,
It uses very extensive.But a large amount of chemical sludge for being rich in molysite at the same time, is also produced, how appropriate must handle disposition
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 for such as electric Fenton of advanced oxidation processes
Method removes 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 being able to achieve H2O2Fabricated in situ and using then can undoubtedly greatly reducing processing cost and environment
Risk.Therefore, if the efficient catalytic of synthesizing new can be regulated and controled by certain means using the sludge rich in molysite as raw material
Agent, fabricated in situ H2O2While in-situ activation H again2O2, realize the mineralising removal of pollutant, then can not only substantially reduce advanced
Novel changing rejected material to useful resource also may be implemented in the operating cost of oxidation technology.
Summary of the invention
A kind of electricity the purpose of the present invention is to provide electric fenton catalyst, cathode and sewage water treatment method, in the present invention
Low energy consumption for fenton catalyst, H2O2Yield is high, mineralization of organic material removal effect is good, realizes the resource utilization of sludge.
The present invention provides a kind of electric fenton catalyst, is made according to the following steps:
A the sludge drying that) will be enriched in molysite, obtains presoma；
B) presoma is heated under protective gas atmosphere to cracking, obtain lysate；
C after lysate) is immersed cleaning in acid solution, drying, 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 cathode, including conductive substrates and the catalyst being 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, obtains cathode after drying.
The present invention provides a kind of sewage water treatment method, comprising the following steps:
It is inserted into sewage in working electrode, to electrode and reference electrode, applies current potential on the working electrode (s, and the drum in sewage
Enter air, the pollutant in sewage of degrading；
The working electrode is cathode 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 the following steps: A) the sludge drying that will be enriched in molysite, it obtains
To presoma；B) presoma is heated under protective gas atmosphere to cracking, obtain lysate；C lysate) is immersed into acid solution
After middle cleaning, drying, electric fenton catalyst is obtained.
The present invention handles to obtain efficiently by the way that the sludged waste material generated during municipal sewage treatment is carried out reprocessing
Electric Fenton cathod catalyst, iron ion and H can added without external source2O2Under conditions of, it is had by catalyst itself
Iron ion, the H generated with electrode autocatalysis reduction oxygen2O2Reaction generates OH free radical, carrys out the organic dirt of efficient mineralization degradation
Object is contaminated, the resource utilization of sludge is realized.Compared with prior art, using the present invention has the advantage that
1, raw material are solid waste, so very big that reduce costs；
2, the elctro-catalyst O obtained2The selectivity and H of reduction2O2Yield is high；
3, load has the electrode of catalyst, and work point is low, further reduced the processing energy consumption of system；
4, H is added without external source2O2Activator, it is so very big that save operating cost.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the preparation flow figure of electric fenton catalyst in the present invention.
Specific embodiment
The present invention provides a kind of electric fenton catalyst, is made according to the following steps:
A the sludge drying that) will be enriched in molysite, obtains presoma；
B) presoma is heated under protective gas atmosphere to cracking, obtain lysate；
C after lysate) is immersed cleaning in acid solution, drying, electric fenton catalyst is obtained.
For the preparation flow of electric fenton catalyst of the invention referring to Fig. 1, Fig. 1 is the preparation of electric fenton catalyst in the present invention
Flow chart.
The present invention preferably by after municipal sewage collection system, adds iron salt coagulant and is handled, and 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 of frerrous chloride, poly-ferric chloride；The iron salt coagulant add concentration be preferably 10~50mg/L (with
Fe meter).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, using the common processing method of those skilled in the art.
After obtaining the sludge rich in molysite, the present invention is baked to, and obtains presoma, and 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 does 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
Rate is preferably 1~10 DEG C/min, more preferably 3~8 DEG C/min, most preferably 5~6 DEG C/min.In cracking item of the invention
The pyrolysis product cracked under part is cracking carbon.
After obtaining lysate, the present invention is dipped in acid solution and cleans, and the impurity such as removal ash content obtain after dry
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 cleanings 2~3 times, then
It is presented again with distilled water flushing to pH value neutral.The drying is preferably dried, 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.
The present invention also provides a kind of cathodes, including conductive substrates and the catalyst being supported in the conductive substrates, institute
Stating catalyst is electric fenton catalyst above.The present invention preferably by the catalyst be scattered in volume fraction be 50~
In 100% alcoholic solution, then add volume fraction be 1~5% Nafion solution to enhance electric conductivity, obtained mixing is molten
Liquid is coated in the surface of conductive substrates, obtains cathode 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 are preferably 30~60 DEG C, and more preferably 40~50 DEG C.
The present invention also provides a kind of methods of sewage treatment, comprising the following steps:
It is inserted into sewage in working electrode, to electrode and reference electrode, applies current potential on the working electrode (s, and the drum in sewage
Enter air, the pollutant in sewage of degrading.
In the present invention, the working electrode is cathode 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, it can be platinum electrode.The present invention comes to the sewage to be processed
Source does not have special limitation, specifically, can be chemical sewage, such as containing the sewage of phenol, can be waste water from dyestuff, such as contains Luo Dan
The waste water of bright B；It can be agricultural chemicals waste water, such as containing the waste water of 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 the following steps: A) the sludge drying that will be enriched in molysite, it obtains
To presoma；B) presoma is heated under protective gas atmosphere to cracking, obtain lysate；C lysate) is immersed into acid solution
After middle cleaning, drying, electric fenton catalyst is obtained.
The present invention handles to obtain efficiently by the way that the sludged waste material generated during municipal sewage treatment is carried out reprocessing
Electric Fenton cathod catalyst, iron ion and H can added without external source2O2Under conditions of, it is had by catalyst itself
Iron ion, the H generated with electrode autocatalysis reduction oxygen2O2Reaction generates OH free radical, carrys out the organic dirt of efficient mineralization degradation
Object is contaminated, the resource utilization of sludge is realized.Compared with prior art, using the present invention has the advantage that
1, raw material are solid waste, so very big that reduce costs；
2, the elctro-catalyst O obtained2The selectivity and H of reduction2O2Yield is high；
3, load has the electrode of catalyst, and work point is low, further reduced the processing energy consumption of system；
4, H is added without external source2O2Activator, it is so very big that save operating cost.
In order to further illustrate the present invention, with reference to embodiments to a kind of electric fenton catalyst, yin provided by the invention
Pole and sewage water treatment method are described in detail, but cannot be understood as limiting the scope of the present invention.
Embodiment 1
It takes the municipal sewage plant 20L to intake, adds iron chloride to above-mentioned according to the concentration of 30mg/L (with Fe ionometer)
In sewage, 20min quickly is stirred at 30rpm again after stirring 2min at 200 rpm, filtering obtains aqueous after staticly settling
The sludge is dried under the conditions of 105 DEG C and moisture removal is gone to obtain presoma by sludge.
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 in blowpipe
Air.Then to 800 DEG C and 6h is maintained according to the heating rate setting temperature programming of 5 DEG C/min.Room temperature is down to tube furnace
The carbon that removal cracking obtains afterwards is cleaned after 3 times repeatedly 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.
It takes 10mg catalyst into 0.5mL75% aqueous isopropanol, ultrasonic disperse after 10 μ LNafion solution is added
Uniform suspension after dispersion must be covered in the carbon paper substrate of 3 × 3cm by 30min, and drying obtains electricity under the conditions of 50 DEG C
Pole.
The application of catalyst: using above-mentioned electrode as working electrode, platinum filament is to electrode, and Ag/AgCl is reference electrode structure
Electro-chemical systems are built, are process object with 50mg/L phenol.It inserts electrodes into 50mL phenol solution, applies 0.25V (vs
RHE) operating potential continuously blasts 200m3/m3/ h air.Catalyst H2O2Average yield can achieve 12.7mmol/h/g,
Phenol can be completely removed in 40min, and TOC removal rate can reach 60% or more in 4h.
Embodiment 2
It takes the municipal sewage plant 20L to intake, adds iron chloride to above-mentioned according to the concentration of 30mg/L (with Fe ionometer)
In sewage, 20min quickly is stirred at 30rpm again after stirring 2min at 200 rpm, filtering obtains aqueous after staticly settling
The sludge is dried under the conditions of 105 DEG C and moisture removal is gone to obtain presoma by sludge.
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 in blowpipe
Air.Then to 600 DEG C and 6h is maintained according to the heating rate setting temperature programming of 5 DEG C/min.After tube furnace is down to room temperature
The carbon that removal cracking obtains is cleaned after 3 times repeatedly 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.
It takes 10mg catalyst into 75% aqueous isopropanol of 0.5mL, ultrasonic disperse after 10 μ LNafion solution is added
Uniform suspension after dispersion must be covered in the carbon paper substrate of 3 × 3cm by 30min, and drying obtains electricity under the conditions of 50 DEG C
Pole.
The application of catalyst: using above-mentioned electrode as working electrode, platinum filament is to electrode, and Ag/AgCl is reference electrode structure
Electro-chemical systems are built, are process object with 50mg/L waste water from dyestuff (rhodamine B).It inserts electrodes into the above-mentioned waste water of 50mL,
Apply 0.25V (vs RHE) operating potential, continuously blasts 200m3/m3/ h air.Catalyst H2O2Average yield can achieve
10mmol/h/g, rhodamine B can be completely removed in 30min, and TOC removal rate can reach 65% or more in 4h.
Embodiment 3
It takes the municipal sewage plant 20L to intake, adds iron chloride to above-mentioned according to the concentration of 30mg/L (with Fe ionometer)
In sewage, 20min quickly is stirred at 30rpm again after stirring 2min at 200 rpm, filtering obtains aqueous after staticly settling
The sludge is dried under the conditions of 105 DEG C and moisture removal is gone to obtain presoma by sludge.
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 in blowpipe
Air.Then to 800 DEG C and 6h is maintained according to the heating rate setting temperature programming of 5 DEG C/min.Room temperature is down to tube furnace
The carbon that removal cracking obtains afterwards is cleaned after 3 times repeatedly 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.
It takes 10mg catalyst into 0.5mL75% aqueous isopropanol, ultrasonic disperse after 10 μ LNafion solution is added
Uniform suspension after dispersion must be covered in the carbon paper substrate of 3 × 3cm by 30min, and drying obtains electricity under the conditions of 50 DEG C
Pole.
The application of catalyst: using above-mentioned electrode as working electrode, platinum filament is to electrode, and Ag/AgCl is reference electrode structure
Electro-chemical systems are built, are process object with 50mg/L pesticide (Atrazine) waste water.It inserts electrodes into 50mL agricultural chemicals waste water,
Apply 0.35V (vs RHE) operating potential, continuously blasts 400m3/m3/ h air.Catalyst H2O2Average yield can achieve
13mmol/h/g, Atrazine can be completely removed in 30min, and TOC removal rate can reach 55% or more in 4h.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of sewage water treatment method, comprising the following steps:
It is inserted into sewage by working electrode, to electrode and reference electrode, applies current potential on the working electrode (s, and blast sky in sewage
Gas, degrade sewage in pollutant；
The working electrode includes conductive substrates and the catalyst that is supported in conductive substrates；
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, what is obtained is mixed
It closes solution and is coated on conductive substrates surface, obtain cathode after drying；
The catalyst is electric fenton catalyst, is made according to the following steps:
A the sludge drying that) will be enriched in molysite, obtains presoma；
B) presoma is heated under protective gas atmosphere to cracking, obtain lysate；
The temperature of the cracking is 600 ~ 800 DEG C；The time of the cracking is 2 ~ 6 hours；
C after lysate) is immersed cleaning in acid solution, drying, electric fenton catalyst is obtained.
2. sewage water treatment method according to claim 1, which is characterized in that the temperature of the drying is 90 ~ 120 DEG C.
3. sewage water treatment method according to claim 1, which is characterized in that the protective gas includes NH3、N2Or Ar.
4. sewage water treatment method according to claim 1, which is characterized in that the acid solution be HCl solution, HF solution or
HClO4Solution；
The mass concentration of the acid solution is 5 ~ 20%.
5. sewage water treatment method according to claim 1, which is characterized in that the current potential of the application is 0.25 ~ 0.45V.
6. sewage water treatment method according to claim 1, which is characterized in that the air-blowing amount of the air is 50 ~ 500m3/
(m3Water h).
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| KR102209270B1 (en) * | 2018-12-14 | 2021-01-29 | 한국과학기술연구원 | Sulfated transition metal oxide catalysts for electro-fenton reaction system, electrode comprising the same and electro-fenton reaction system using the 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 |
| CN112064084B (en) * | 2020-08-06 | 2022-10-25 | 陕西科技大学 | Preparation method of metal monoatomic titanium suboxide electrode |
| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502842A (en) * | 2016-01-19 | 2016-04-20 | 东华大学 | Wastewater Fenton oxidation-biological combined treatment method and device capable of recycling sludge |
| CN106025296A (en) * | 2016-07-27 | 2016-10-12 | 同济大学 | Nitrogen-phosphorus double-doped carbon material as well as preparation method and application thereof |
| CN106944053A (en) * | 2017-02-14 | 2017-07-14 | 浙江省农业科学院 | A kind of sludge carbon base type Fenton catalyst and its preparation method and application |
-
2017
- 2017-08-01 CN CN201710648455.8A patent/CN107335435B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502842A (en) * | 2016-01-19 | 2016-04-20 | 东华大学 | Wastewater Fenton oxidation-biological combined treatment method and device capable of recycling sludge |
| CN106025296A (en) * | 2016-07-27 | 2016-10-12 | 同济大学 | Nitrogen-phosphorus double-doped carbon material as well as preparation method and application thereof |
| CN106944053A (en) * | 2017-02-14 | 2017-07-14 | 浙江省农业科学院 | A kind of sludge carbon base type Fenton catalyst and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| "An efficient sewage sludge-derived bi-functional electrocatalyst for oxygen reduction and evolution reaction";Shi-Jie Yuan等;《Royal Society of Chemistry》;20160414;第18卷;第4004-4011页 * |
| "Three-dimensional heterogeneous electro-Fenton oxidation of biologically pretreated coal gasification wastewater using sludge derived carbon as catalytic particle electrodes and catalyt";BaolinHou等;《Journal of the Taiwan Institute of Chemical Engineers》;20151114;第60卷;第352-360页 * |
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