CN106540672A - A kind of magnetic porous sludge carbon carries metal oxide catalyst and its reacts the application in degraded azo dye in persulfate oxidation - Google Patents
A kind of magnetic porous sludge carbon carries metal oxide catalyst and its reacts the application in degraded azo dye in persulfate oxidation Download PDFInfo
- Publication number
- CN106540672A CN106540672A CN201611118167.3A CN201611118167A CN106540672A CN 106540672 A CN106540672 A CN 106540672A CN 201611118167 A CN201611118167 A CN 201611118167A CN 106540672 A CN106540672 A CN 106540672A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- sludge carbon
- sludge
- metal oxide
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010802 sludge Substances 0.000 title claims abstract description 99
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 34
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 31
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 26
- 239000000987 azo dye Substances 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- -1 be then dried Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000010865 sewage Substances 0.000 claims description 7
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000003415 peat Substances 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 238000004043 dyeing Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000000975 dye Substances 0.000 abstract description 4
- 230000029087 digestion Effects 0.000 abstract description 3
- 150000001455 metallic ions Chemical class 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 2
- 239000003622 immobilized catalyst Substances 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 13
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007337 electrophilic addition reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000009992 mercerising Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/72—Copper
-
- 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
- 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
- B01J23/75—Cobalt
-
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J37/0207—Pretreatment of the support
-
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to immobilized catalyst, dyestuff contaminant are removed, solid waste such as utilizes at the technical field, more particularly to a kind of magnetic porous sludge carbon carries metal oxide catalyst and its reacts the application in degraded azo dye in persulfate oxidation.Magnetic porous sludge carbon carries metal oxide catalyst, is made up of sludge carbon and metal-oxide, and metal ion weight/mass percentage composition in the catalyst is 1～3%.The present invention prepares sludge carbon by carbonization treatment, then with sludge carbon as carrier first with remaining municipal sludge, slaine as raw material, metal ion is loaded on sludge carbon, metal oxide catalyst is carried through preparing sludge carbon, the preparation method of the catalyst is simple, cheap.The catalysis activity of the catalyst is high, and digestion of metallic ion is low, good stability.Heterogeneous persulfate oxidation technical finesse dyeing waste water is applied to the catalyst, can be carried out at ambient temperature, reaction condition is gentle, good decolorizing effect.
Description
Technical field
The present invention relates to immobilized catalyst, dyestuff contaminant are removed, solid waste such as utilizes at the technical field, more particularly to it is a kind of
Magnetic porous sludge carbon carries metal oxide catalyst and its reacts the application in degraded azo dye in persulfate oxidation.
Background technology
Dyeing waste water is essentially from desizing, boiling-off, bleaching, mercerising, dyeing, stamp, finishing section, this kind of chroma in waste water
Greatly, organic components are complicated and content is high, and traditional water technology is difficult to reach desired treatment effect to this kind of waste water, should
The Processing Technology Research of class waste water is the difficult point and focus of wastewater treatment research.
With the rising of sewage treatment capacity, the surplus sludge volume that biochemical processing process is produced in sewage disposal process
It is constantly soaring.Excess sludge moisture content is high, and complicated component, its property are unstable, and easily corruption produces foul smell, if process disposing not
When the secondary pollution that certainly will cause environment.Therefore, how Sciences Economics ground carries out processing disposing to these excess sludges is equally
The difficult point and focus of wastewater treatment.
High-level oxidation technology is a kind of efficient wastewater processing technology and receives much concern and research be gradually developed.It leads
Or to be passed through using reacting the free radical for producing as oxidant by the mode mineralising organic pollutants such as electrophilic addition reaction
The direct oxidation of itself improves the biodegradability of pollutant.With traditional water technology Comparatively speaking, high-level oxidation technology tool
Active high, oxidability is extremely strong, and reaction rate is exceedingly fast, and selectivity is less, for the organic pollution effect for processing complexity
Substantially, can be by organic pollution mineralizing and degrading complicated in water.High-level oxidation technology can be divided into Fenton oxidation method, ozone oxidation
Method, photocatalytic oxidation, Wet Catalytic Oxidation Method, electrochemical catalysis method, persulfate oxidation etc..
In high-level oxidation technology, persulfate oxidation method is based on potentiometric titrations (SO4 -) a kind of new height
Level oxidation technology.Persulfate ionizable generation persulfate ion S in the reaction2O8 2-, containing oxidizing stronger in its molecule
Dioxygen key O-O, its standard oxidationreduction potential be E0=+2.01V, is close to O3(E0=+2.07V).But due to persulfate ratio
More stable, reaction rate is slower at normal temperatures, unobvious to the degradation effect of pollutant, need to be in light and heat (h γ), transition metal
(Mn+) etc. under the conditions of catalytic activation.S2O8 2-Can activate and be decomposed into SO4 -, SO4 -Standard oxidationreduction potential E0=+2.5～
+ 3.1V, close to even more than OH (E0=+1.8～+2.7V), can be by most organic pollutants degraded while mineralising
For CO2And mineral acid.Therefore persulfate oxidation method is the high-level oxidation technology based on sulphuric acid free radical, with stable reaction,
Mild condition, it is simple to operate, the advantage such as non-secondary pollution thing and be concerned and study.
The present invention is combined with persulfate using prepared sludge carbon metal oxide supporting catalyst, constitutes new height
Level oxidation technology characteristic, the orange II stimulated dye wastewaters of azo dyes have reached good removal effect, and solid-phase catalyst
Digestion of metallic ion is low, and technological process is simple, and low cost carries out recycling to garbage, before fine practice
Scape.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of cheap, resource, callable catalyst, and its
Utilization on degradable organic pollutant.Particularly, the invention provides a kind of magnetic porous sludge carbon load metal-oxide is urged
Agent and its application in persulfate oxidation reaction degraded azo dye.
To solve above-mentioned technical problem, the technical solution used in the present invention is：
A kind of magnetic porous sludge carbon carries metal oxide catalyst, is made up of sludge carbon and metal-oxide, metal from
Son weight/mass percentage composition in the catalyst is 1～3%.
Preferably, the metal ion is cobalt, ferrum or copper ion.
It is a kind of to prepare the method that magnetic porous sludge carbon carries metal oxide catalyst, made by with municipal sludge as raw material
Sludge carbon is fixed in sludge carbon by equi-volume impregnating as carrier, metal ion, is obtained with magnetic porous sludge
Charcoal carries metal oxide catalyst.
Preferably, preparation method is comprised the following steps that：
1) municipal sludge, is taken, pickling, washing, drying, grinding are sieved and obtain dewatered sludge powder；
2), dewatered sludge powder is mixed with organic acid template solution, carbonization treatment is carried out after being dried and is obtained sludge carbon；
3), sludge carbon is mixed with soluble metal salt solution class activator, is vibrated with impregnating metal ion, Ran Hougan
Dry, carbonization treatment obtains catalyst.
Further, step 1) concrete operations are：Sewage treatment plant residual sludge is soaked into 24h with hydrochloric acid solution, so
After filter, deionized water is washed till neutrality, is put in baking oven and dries at 105 DEG C, ground 100 mesh sieve.
Step 2) concrete operations are：Dewatered sludge powder is mixed into (dewatered sludge powder with the citric acid solution of 0.1～0.2mol/L
Mass ratio 1 between end and citric acid：2), magnetic agitation mixes heat drying, then moves in tube furnace, in nitrogen atmosphere
300～600 DEG C are warming up under (100mL/min, programming rate are 10 DEG C/min), 2～6h is calcined, then nitrogen protection drops to
Room temperature, obtains sludge carbon.
Step 3) concrete operations are：Sludge carbon is mixed with soluble metal salt solution class activator, the vibration leaching at 25 DEG C
Stain 24h, dries in being then placed in baking oven at 105 DEG C, grind into powder, finally moves in tube furnace, in nitrogen atmosphere
300～600 DEG C are warming up under (100mL/min, programming rate are 10 DEG C/min), 2～6h is calcined, then nitrogen protection drops to
Room temperature, obtains magnetic porous sludge carbon and carries metal oxide catalyst；The cation of soluble metallic salt be cobalt, ferrum or copper from
Son, metal ion weight/mass percentage composition in the catalyst are 1～3%.
A kind of magnetic porous sludge carbon carries metal oxide catalyst in persulfate oxidation reaction degraded azo dye
Application, persulfate oxidation reaction degraded azo dye during, using magnetic porous sludge carbon carry metal-oxide make
It is catalyst with accelerated degradation process.
A kind of magnetic porous sludge carbon carries metal oxide catalyst in the persulfate oxidation for azo dye of degrading
Application in reactor, persulfate oxidation reactor are tapered, carry out reaction stirring using agitator, and reactor adopts magnetic
Absorption or membrance separation mode separating catalyst；In azo dye, add persulfate and sludge carbon to carry metal oxide oxidation catalyst
Agent, by the degradation process of the reactor for treatment azo dyes, after the completion of degraded, will be catalyzed by magnetic absorption or membrance separation
Agent is separated from reaction system, back and forth to recycle.Specifically, by the dyeing waste water containing azo dye, this is placed in reaction
In device, after being initially charged persulfate, it is added immediately sludge carbon and carries metal oxide catalyst, it is organic in reaction treatment dyeing waste water
Pollutant.
Advantage for present invention with effect is：
1), the present invention prepares sludge carbon by carbonization treatment first with remaining municipal sludge, slaine as raw material,
Then with sludge carbon as carrier, metal ion is loaded on sludge carbon, is urged through preparing sludge carbon load metal-oxide
Agent, the preparation method of the catalyst are simple, cheap.The catalysis activity of the catalyst is high, and digestion of metallic ion is low, stable
Property is good.Heterogeneous persulfate oxidation technical finesse dyeing waste water is applied to the catalyst, can be carried out at ambient temperature, instead
Answer mild condition, good decolorizing effect.
2), magnetic porous sludge carbon of the invention carries metal oxide catalyst as a kind of persulfate catalyst, its
Preparation method is simple, and material has magnetic porous, can recycle, in catalysis persulfate oxidation reactor, to azo
The degradation efficiency of dyestuff is high, non-secondary pollution, and only in waste water, persistent organic pollutants do not provide new technology, are also dirt
The recycling of peat provides a new approach, while novel reactor is realized catalyst is recycled, to ring
Border protection is significant.
Description of the drawings
The invention will be further described below in conjunction with the accompanying drawings：
Fig. 1 a～c is the SEM figures of catalyst prepared by embodiment 1～3.
Fig. 2 is that sludge carbon prepared by embodiment 1～3 carries metal oxide catalyst with reference to persulfate system to acid orange
The clearance curve of II.
Specific embodiment
Embodiment 1
A kind of magnetic porous sludge carbon carries cobalt oxide catalyst, and in catalyst, the weight/mass percentage composition of cobalt is 1%, its system
Preparation Method is：
1) sewage treatment plant residual sludge is soaked into 24h with hydrochloric acid solution, is then filtered, deionized water is washed till neutrality, puts
Dry at 105 DEG C in entering baking oven, ground 100 mesh sieve obtains dewatered sludge powder.
2) dewatered sludge powder is mixed into (the matter between dewatered sludge powder and citric acid with the citric acid solution of 0.1mol/L,
Amount compares 1：2), magnetic agitation mixes heat drying, then moves in tube furnace, in nitrogen atmosphere (100mL/min, programming rate
For 10 DEG C/min) under be warming up to 300 DEG C, calcine 6h, then nitrogen protection drop to room temperature, obtain sludge carbon.
3) cobalt nitrate hexahydrate (Co (NO of 0.5g, are weighed3)2·6H2O, molecular weight are 291) plus 19.5mL ultra-pure waters, molten
Solution obtains cobalt liquor in beaker.The sludge carbon for taking 10g is put in beaker, adds 20mL cobalt liquors, 25 DEG C of isothermal vibration dippings
24h, obtains being impregnated with the sludge carbon of cobalt.
4), the sludge carbon for being impregnated with cobalt is put in baking oven and is dried at 105 DEG C, grind into powder finally moves into tubular type
In stove, 400 DEG C being warming up under nitrogen atmosphere (100mL/min, programming rate are 10 DEG C/min), calcining 3h, then nitrogen is protected
Shield drops to room temperature, obtains magnetic porous sludge carbon and carries cobalt oxide catalyst.
Embodiment 2
A kind of magnetic porous sludge carbon carries ferriferous oxide catalyst, and in catalyst, the weight/mass percentage composition of ferrum is 2%, its system
Preparation Method is：
1) sewage treatment plant residual sludge is soaked into 24h with hydrochloric acid solution, is then filtered, deionized water is washed till neutrality, puts
Dry at 105 DEG C in entering baking oven, ground 100 mesh sieve obtains dewatered sludge powder.
2) dewatered sludge powder is mixed into (the matter between dewatered sludge powder and citric acid with the citric acid solution of 0.15mol/L,
Amount compares 1：2), magnetic agitation mixes heat drying, then moves in tube furnace, in nitrogen atmosphere (100mL/min, programming rate
For 10 DEG C/min) under be warming up to 400 DEG C, calcine 3h, then nitrogen protection drop to room temperature, obtain sludge carbon.
3) the nine water ferric nitrate (Fe (NO of 1.4g, are weighed3)3·9H2O, molecular weight are 404) plus 18.6mL ultra-pure waters, molten
Solution obtains ferrous solution in beaker.The sludge carbon for taking 10g is put in beaker, adds 20mL ferrous solutions, 25 DEG C of isothermal vibration dippings
24h, obtains being impregnated with the sludge carbon of ferrum.
4), the sludge carbon for being impregnated with ferrum is put in baking oven and is dried at 105 DEG C, grind into powder finally moves into tubular type
In stove, 500 DEG C being warming up under nitrogen atmosphere (100mL/min, programming rate are 10 DEG C/min), calcining 2h, then nitrogen is protected
Shield drops to room temperature, obtains magnetic porous sludge carbon and carries ferriferous oxide catalyst.
Embodiment 3
A kind of copper-loaded oxide catalyst of magnetic porous sludge carbon, in catalyst, the weight/mass percentage composition of copper is 3%, its system
Preparation Method is：
1) sewage treatment plant residual sludge is soaked into 24h with hydrochloric acid solution, is then filtered, deionized water is washed till neutrality, puts
Dry at 105 DEG C in entering baking oven, ground 100 mesh sieve obtains dewatered sludge powder.
2) dewatered sludge powder is mixed into (the matter between dewatered sludge powder and citric acid with the citric acid solution of 0.2mol/L,
Amount compares 1：2), magnetic agitation mixes heat drying, then moves in tube furnace, in nitrogen atmosphere (100mL/min, programming rate
For 10 DEG C/min) under be warming up to 500 DEG C, calcine 2.5h, then nitrogen protection drop to room temperature, obtain sludge carbon.
3) the nitrate trihydrate copper (Cu (NO of 1.2g, are weighed3)2·3H2O, molecular weight are 242) plus 18.8mL ultra-pure waters, molten
Solution obtains copper solution in beaker.The sludge carbon for taking 10g is put in beaker, adds 20mL copper solutions, 25 DEG C of isothermal vibration dippings
24h, obtains being impregnated with the sludge carbon of copper.
4), the sludge carbon for being impregnated with copper is put in baking oven and is dried at 105 DEG C, grind into powder finally moves into tubular type
In stove, 600 DEG C are warming up under nitrogen atmosphere (100mL/min, programming rate be 10 DEG C/min), carbonization treatment 2h, then nitrogen
Gas shielded drops to room temperature, obtains the copper-loaded oxide catalyst of magnetic porous sludge carbon.
Product characterizes and degrades test
1st, product is characterized
The SEM of catalyst prepared by embodiment 1～3 schemes respectively as shown in Fig. 1 a～c, as seen in Figure 1, sludge carbon
Carry metal oxide catalyst in the form of sheets or graininess, surface has porous.
2nd, degraded test
Sludge carbon carries application of the metal oxide catalyst in degraded azo dye, and specific application process includes following
Step：
1), configuration concentration is 100mg/L Acid Orange II solution 50mL, is positioned in conical flask, is initially charged the persulfuric acid of 2g
Sodium, add afterwards 2g sludge carbons carry metal oxide catalyst (catalyst that prepared using embodiment 1～3 and blank as
Four groups of experiments), to shake speed as 150r/min oscillation treatment 12min under shaking table.
2) after, completing oscillation treatment, Acid Orange II solution 2mL after treatment is taken, adds the methanol solution of 1mL, eventually
Only catalytic reaction, is filtered with syringe filter, using the concentration of spectrophotometer measurement Acid Orange II.
Fig. 2 is that sludge carbon prepared by embodiment 1～3 carries metal oxide catalyst with reference to persulfate system to acid orange
The clearance curve of II.From figure 2 it can be seen that carrying metal oxide catalyst joint persulfate pair using sludge carbon
The clearance of 100mg/L Acid Orange IIs reaches more than 98%.
The present invention is not limited to above-described embodiment, and embodiment is exemplary, it is intended to for explaining the present invention, and can not
It is interpreted as limitation of the present invention.
Claims (9)
1. a kind of magnetic porous sludge carbon carries metal oxide catalyst, it is characterised in that by sludge carbon and metal-oxide group
Into metal ion weight/mass percentage composition in the catalyst is 1～3%.
2. catalyst as claimed in claim 1, it is characterised in that the metal ion is cobalt, ferrum or copper ion.
3. a kind of method for preparing catalyst as claimed in claim 1 or 2, it is characterised in that be made up with municipal sludge of raw material
Sludge carbon as carrier, metal ion is fixed in sludge carbon by equi-volume impregnating, is obtained with magnetic porous dirt
Peat carries metal oxide catalyst.
4. preparation method as claimed in claim 3, it is characterised in that comprise the following steps that：
1) municipal sludge, is taken, pickling, washing, drying, grinding are sieved and obtain dewatered sludge powder；
2), dewatered sludge powder is mixed with organic acid template solution, carbonization treatment is carried out after being dried and is obtained sludge carbon；
3), sludge carbon is mixed with soluble metal salt solution class activator, is vibrated with impregnating metal ion, be then dried, carbon
Change is processed and obtains catalyst.
5. preparation method as claimed in claim 4, it is characterised in that step 1) concrete operations are：By sewage treatment plant residual
Sludge soaks 24h with hydrochloric acid solution, then filters, and deionized water is washed till neutrality, dries, grinding in being put into baking oven at 105 DEG C
Cross 100 mesh sieves.
6. preparation method as claimed in claim 4, it is characterised in that step 2) concrete operations are：By dewatered sludge powder and 0.1
The citric acid solution mixing of～0.2mol/L, magnetic agitation mix heat drying, then move in tube furnace, in a nitrogen atmosphere
300～600 DEG C are warming up to, 2～6h is calcined, then nitrogen protection drops to room temperature, obtains sludge carbon.
7. preparation method as claimed in claim 4, it is characterised in that step 3) concrete operations are：Sludge carbon and solubility gold
Category saline solution class activator mixing, the vibration dipping 24h at 25 DEG C, dries at 105 DEG C in being then placed in baking oven, pulverizes
End, finally moves in tube furnace, is warming up to 300～600 DEG C in a nitrogen atmosphere, calcines 2～6h, and then nitrogen protection drops to
Room temperature, obtains magnetic porous sludge carbon and carries metal oxide catalyst；The cation of soluble metallic salt be cobalt, ferrum or copper from
Son, metal ion weight/mass percentage composition in the catalyst are 1～3%.
8. a kind of sludge carbon magnetic porous as claimed in claim 1 carries metal oxide catalyst and drops in persulfate oxidation reaction
Application in solution azo dye, it is characterised in that during persulfate oxidation reaction degraded azo dye, many using magnetic
Hole sludge carbon carries metal-oxide as catalyst with accelerated degradation process.
9. a kind of sludge carbon magnetic porous as claimed in claim 1 carries metal oxide catalyst for azo dye of degrading
Application in persulfate oxidation reactor, it is characterised in that persulfate oxidation reactor is tapered, is carried out using agitator
Reaction stirring, reactor adopt magnetic absorption or membrance separation mode separating catalyst；In azo dye add persulfate and
Sludge carbon carries metal oxide catalyst, by the degradation process of the reactor for treatment azo dyes, after the completion of degraded, passes through
Catalyst is separated from reaction system by magnetic absorption or membrance separation, back and forth to recycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611118167.3A CN106540672A (en) | 2016-12-07 | 2016-12-07 | A kind of magnetic porous sludge carbon carries metal oxide catalyst and its reacts the application in degraded azo dye in persulfate oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611118167.3A CN106540672A (en) | 2016-12-07 | 2016-12-07 | A kind of magnetic porous sludge carbon carries metal oxide catalyst and its reacts the application in degraded azo dye in persulfate oxidation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106540672A true CN106540672A (en) | 2017-03-29 |
Family
ID=58396468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611118167.3A Pending CN106540672A (en) | 2016-12-07 | 2016-12-07 | A kind of magnetic porous sludge carbon carries metal oxide catalyst and its reacts the application in degraded azo dye in persulfate oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106540672A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109570222A (en) * | 2018-11-29 | 2019-04-05 | 南京工业大学 | The method that magnetic sludge carbon strengthens electronic-chemical oxidation renovation of organic pollution soil |
| CN110116000A (en) * | 2019-04-04 | 2019-08-13 | 杭州师范大学 | A kind of sludge carbon-supported catalysts and its preparation method and application |
| CN110171876A (en) * | 2019-05-16 | 2019-08-27 | 浙江科技学院 | A kind of N doping sludge carbon carries the preparation method and applications of nano ferriferrous oxide |
| CN110372510A (en) * | 2019-07-29 | 2019-10-25 | 南京师范大学 | A method of Arylacetic acids ester derivant is catalyzed and synthesized using surface modified sewage sludge charcoal |
| CN110606539A (en) * | 2019-10-16 | 2019-12-24 | 河南省科学院化学研究所有限公司 | Method for treating organic wastewater by utilizing sludge resource |
| CN111437825A (en) * | 2020-05-28 | 2020-07-24 | 广东工业大学 | Iron-manganese biochar catalyst and application thereof in conditioning sludge dehydration |
| CN112058265A (en) * | 2020-09-18 | 2020-12-11 | 昆明理工大学 | Preparation method and application of paper mill sludge activated carbon supported CU-CO catalyst |
| CN112094679A (en) * | 2020-08-12 | 2020-12-18 | 怀宁县泰华新能源科技有限公司 | Biomass granular fuel with high combustion performance and preparation method thereof |
| CN113058631A (en) * | 2021-03-19 | 2021-07-02 | 天津大学 | Preparation method and application of sludge-red mud compound biochar containing Fe-C-O-N active sites |
| CN113842956A (en) * | 2021-10-29 | 2021-12-28 | 合肥工业大学 | Preparation method and application of carbon-based packaging cobalt oxide magnetic material |
| CN113976166A (en) * | 2021-11-09 | 2022-01-28 | 广西民族大学 | Preparation method and application of nitrogen-doped ordered mesoporous carbon catalyst |
| CN114471562A (en) * | 2021-12-28 | 2022-05-13 | 浙江大学 | Metal self-doped sludge carbon-based catalytic material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500376A (en) * | 2011-10-24 | 2012-06-20 | 武汉大学 | Activated carbon loaded iron-cobalt oxide catalyst and application thereof in degrading organic pollutants |
| CN103406094A (en) * | 2013-06-04 | 2013-11-27 | 北京林业大学 | Method for manufacturing magnetic sludge-based active carbon |
| WO2014027953A1 (en) * | 2012-08-17 | 2014-02-20 | Su Holding Ab | Magnetic activated carbon and methods for preparing and regenerating such materials |
| CN106076256A (en) * | 2016-07-06 | 2016-11-09 | 中山大学 | A kind of preparation method and applications of nanometer Fe (0) porous mud material with carbon element |
-
2016
- 2016-12-07 CN CN201611118167.3A patent/CN106540672A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500376A (en) * | 2011-10-24 | 2012-06-20 | 武汉大学 | Activated carbon loaded iron-cobalt oxide catalyst and application thereof in degrading organic pollutants |
| WO2014027953A1 (en) * | 2012-08-17 | 2014-02-20 | Su Holding Ab | Magnetic activated carbon and methods for preparing and regenerating such materials |
| CN103406094A (en) * | 2013-06-04 | 2013-11-27 | 北京林业大学 | Method for manufacturing magnetic sludge-based active carbon |
| CN106076256A (en) * | 2016-07-06 | 2016-11-09 | 中山大学 | A kind of preparation method and applications of nanometer Fe (0) porous mud material with carbon element |
Non-Patent Citations (1)
| Title |
|---|
| LINGJUN KONG,ET AL: "Sorption performance and mechanism of a sludge-derived char as porous carbon-based hybrid adsorbent for benzene derivatives in aqueous solution", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109570222A (en) * | 2018-11-29 | 2019-04-05 | 南京工业大学 | The method that magnetic sludge carbon strengthens electronic-chemical oxidation renovation of organic pollution soil |
| CN110116000A (en) * | 2019-04-04 | 2019-08-13 | 杭州师范大学 | A kind of sludge carbon-supported catalysts and its preparation method and application |
| CN110171876A (en) * | 2019-05-16 | 2019-08-27 | 浙江科技学院 | A kind of N doping sludge carbon carries the preparation method and applications of nano ferriferrous oxide |
| CN110171876B (en) * | 2019-05-16 | 2021-12-21 | 浙江科技学院 | Preparation method and application of nitrogen-doped sludge carbon-supported nano ferroferric oxide |
| CN110372510A (en) * | 2019-07-29 | 2019-10-25 | 南京师范大学 | A method of Arylacetic acids ester derivant is catalyzed and synthesized using surface modified sewage sludge charcoal |
| CN110372510B (en) * | 2019-07-29 | 2022-05-20 | 南京师范大学 | Method for catalytically synthesizing aryl acetate derivative by utilizing surface modified sludge carbon |
| CN110606539B (en) * | 2019-10-16 | 2021-10-15 | 河南省科学院化学研究所有限公司 | Method for treating organic wastewater by utilizing sludge resource |
| CN110606539A (en) * | 2019-10-16 | 2019-12-24 | 河南省科学院化学研究所有限公司 | Method for treating organic wastewater by utilizing sludge resource |
| CN111437825A (en) * | 2020-05-28 | 2020-07-24 | 广东工业大学 | Iron-manganese biochar catalyst and application thereof in conditioning sludge dehydration |
| CN111437825B (en) * | 2020-05-28 | 2023-06-20 | 广东工业大学 | Iron-manganese biochar catalyst and application thereof in conditioning sludge dewatering |
| CN112094679A (en) * | 2020-08-12 | 2020-12-18 | 怀宁县泰华新能源科技有限公司 | Biomass granular fuel with high combustion performance and preparation method thereof |
| CN112094679B (en) * | 2020-08-12 | 2021-12-24 | 怀宁县泰华新能源科技有限公司 | Biomass granular fuel with high combustion performance and preparation method thereof |
| CN112058265A (en) * | 2020-09-18 | 2020-12-11 | 昆明理工大学 | Preparation method and application of paper mill sludge activated carbon supported CU-CO catalyst |
| CN113058631A (en) * | 2021-03-19 | 2021-07-02 | 天津大学 | Preparation method and application of sludge-red mud compound biochar containing Fe-C-O-N active sites |
| CN113842956A (en) * | 2021-10-29 | 2021-12-28 | 合肥工业大学 | Preparation method and application of carbon-based packaging cobalt oxide magnetic material |
| CN113842956B (en) * | 2021-10-29 | 2024-04-02 | 合肥工业大学 | Preparation method and application of carbon-based encapsulated cobalt oxide magnetic material |
| CN113976166A (en) * | 2021-11-09 | 2022-01-28 | 广西民族大学 | Preparation method and application of nitrogen-doped ordered mesoporous carbon catalyst |
| CN113976166B (en) * | 2021-11-09 | 2023-09-15 | 广西民族大学 | Preparation method and application of nitrogen-doped ordered mesoporous carbon catalyst |
| CN114471562A (en) * | 2021-12-28 | 2022-05-13 | 浙江大学 | Metal self-doped sludge carbon-based catalytic material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106540672A (en) | A kind of magnetic porous sludge carbon carries metal oxide catalyst and its reacts the application in degraded azo dye in persulfate oxidation | |
| CN109675581B (en) | Ferro-manganese bimetal oxide modified biochar photo-Fenton composite material and preparation method thereof | |
| CN105668759B (en) | A method of recycling Fenton iron mud | |
| CN109894115A (en) | A kind of preparation method of the modified active carbon catalyst for the processing of class Fenton | |
| CN112156752B (en) | Modified activated carbon with reproducible adsorbability and application thereof in wastewater treatment | |
| CN102941084A (en) | Method for preparing double-component metallic oxide catalytic ozonation catalyst | |
| CN111620431A (en) | Application of adsorbed-desorbed waste biochar in degradation of persistent organic pollutants by activated persulfate | |
| CN107413835B (en) | Method for restoring petroleum polluted soil | |
| CN110665512B (en) | Manganese dioxide-magnetic biochar composite catalyst and preparation method and application thereof | |
| CN110694691A (en) | photo-Fenton catalyst, preparation method and application method | |
| CN108380214B (en) | A kind of preparation of modified meerschaum and method applied to wastewater treatment | |
| CN109095590A (en) | LaFe1-xCuxO3The method for handling residue in water Atrazine | |
| CN108607507A (en) | A kind of preparation method of the high stability charcoal base cementite of degradation of dye | |
| CN104289250A (en) | Loaded type ozone catalyst and preparation method and application thereof | |
| CN106892482A (en) | A kind of black TiO2Nano material and preparation method and application | |
| CN110152702A (en) | Derivative nitrogen carbon nanomaterial of a kind of organic backbone and its preparation method and application | |
| CN112340830B (en) | Application of catalyst taking waste adsorbent after adsorption-desorption as raw material in treating high-salt organic wastewater by activating persulfate | |
| CN105233838A (en) | Preparation method of O3/H2O2 catalyst using activated bentonite as carrier, catalyst and application thereof | |
| CN111617761A (en) | Magnetic sewage peat heterogeneous Fenton catalyst and preparation method thereof | |
| CN106744952A (en) | The method that sewage sludge prepares modified active coke | |
| CN110092438B (en) | Method for treating organic wastewater by using electrolytic manganese residues as photocatalyst | |
| CN112473652A (en) | Preparation method and application of hydrogen peroxide modified biochar containing transition metal | |
| CN103691448B (en) | The preparation method of magnetic sludge base ozone catalyst and application | |
| CN110342701A (en) | A kind of non-biochemical method processing Landfill Leachate technique | |
| CN113457691B (en) | Gold-silver alloy nano flower water treatment catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170329 |