CN107827195A - A kind of method of absorption method photocatalytic degradation method Combined Treatment organic dye waste water - Google Patents
A kind of method of absorption method photocatalytic degradation method Combined Treatment organic dye waste water Download PDFInfo
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- CN107827195A CN107827195A CN201711040915.5A CN201711040915A CN107827195A CN 107827195 A CN107827195 A CN 107827195A CN 201711040915 A CN201711040915 A CN 201711040915A CN 107827195 A CN107827195 A CN 107827195A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 76
- 239000010919 dye waste Substances 0.000 title claims abstract description 31
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 23
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000002071 nanotube Substances 0.000 claims abstract description 57
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 52
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 46
- 239000010439 graphite Substances 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- 239000003463 adsorbent Substances 0.000 claims abstract description 25
- 239000006228 supernatant Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 10
- 230000015556 catabolic process Effects 0.000 claims abstract description 8
- 238000006731 degradation reaction Methods 0.000 claims abstract description 8
- 238000005286 illumination Methods 0.000 claims abstract description 8
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 42
- 239000006185 dispersion Substances 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- 238000007254 oxidation reaction Methods 0.000 claims description 35
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 21
- 230000008021 deposition Effects 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 21
- 229910052697 platinum Inorganic materials 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 17
- 229910000859 α-Fe Inorganic materials 0.000 claims description 15
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 14
- 238000002484 cyclic voltammetry Methods 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 13
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical class CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims description 5
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- HVOTUKZHYGHCBK-UHFFFAOYSA-N C(C)N1CN(C=C1)C.C(C)S(=O)(=O)O Chemical class C(C)N1CN(C=C1)C.C(C)S(=O)(=O)O HVOTUKZHYGHCBK-UHFFFAOYSA-N 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 235000009508 confectionery Nutrition 0.000 claims 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims 1
- 229910052753 mercury Inorganic materials 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 238000004042 decolorization Methods 0.000 abstract description 4
- -1 graphite Alkene Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000012266 salt solution Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 241000446313 Lamella Species 0.000 description 6
- 229940075397 calomel Drugs 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 6
- 230000003111 delayed effect Effects 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000000975 dye Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FPXVXEIZGKLUIX-UHFFFAOYSA-M ethanol;hexadecyl(trimethyl)azanium;bromide Chemical compound [Br-].CCO.CCCCCCCCCCCCCCCC[N+](C)(C)C FPXVXEIZGKLUIX-UHFFFAOYSA-M 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/39—Photocatalytic properties
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- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- 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
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- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a kind of method of absorption method photocatalytic degradation method Combined Treatment organic dye waste water, graphite oxide/porous carbon ball compound adsorbent is prepared first；Then Cu is prepared2O/ graphenes/α Fe2O3Nano-tube array compound；Finally organic dye waste water is removed the gred through grid after just precipitating, supernatant is pumped into the adsorption treatment pond equipped with compound adsorbent, stirring and adsorbing handles 1 3h at 30 DEG C, then staticly settles, the supernatant after precipitation is pumped into reactor；Cu obtained above is added into reactor2O/ graphenes/α Fe2O3Nano-tube array compound is pumped into air as catalyst, the 16h of degradation treatment 10 under illumination condition, then the 6h of stir process 4 in the dark state, finally staticly settles, supernatant reaches discharge standard.Method percent of decolourization disclosed by the invention is high, and COD clearances are high, and cost is low.
Description
Technical field：
The present invention relates to Organic Dyestuff Wastewater Treatment field, is specifically related to a kind of absorption method-photocatalytic degradation method joint
The method for handling organic dye waste water.
Background technology：
Dyestuff is a kind of important fine chemical product, closely related with the clothing, food, lodging and transportion -- basic necessities of life of the mankind.With dye industry
Fast development, it produces waste water has turned into one of current most important pollution source of water body.Because dye species are various, production work
Skill, dyeing are different, and caused wastewater flow rate and composition also vary, but water quality characteristic shows as high concentration, height
Colourity, high COD and BOD values, so its Treatment process is always the difficult point of Industrial Wastewater Treatment.Processing method bag main at present
Physical, chemical method, bioanalysis, physical-chemical process are included, usually various methods are used in combination in actual treatment method could more
The good harmful substance removed in waste water.
The content of the invention：
It is an object of the invention to provide a kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water,
This method can effectively handle the harmful substance in waste water, and percent of decolourization is high, low to water body non-secondary pollution, processing cost.
To achieve the above object, the present invention uses following technical scheme：
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, comprises the following steps：
(1) weigh graphite oxide to be added in deionized water, be ultrasonically treated 1h under 500W power, obtain graphite oxide and disperse
Liquid；
(2) porous carbon ball is placed in the ethanol solution of cetyl trimethylammonium bromide, stirred at 30-40 DEG C
30-70min is handled, after processing terminates, filtering, obtained solid vacuum drying, pretreatment porous carbon ball is made；
(3) graphite oxide dispersion obtained above and pretreatment porous carbon ball are mixed and be transferred in three-necked flask, delayed
Slow to be warming up to 80-90 DEG C, reflow treatment 5h under 3000rpm, processing is cooled to room temperature after terminating, centrifugal treating is heavy after centrifugation
Shallow lake drying, obtains compound adsorbent；
(4) high-purity iron plate is polished, then cleaned successively in absolute ethyl alcohol and distilled water, dried, it is standby；With above-mentioned place
High-purity iron plate after reason is negative electrode as anode, platinized platinum, and the ethylene glycol solution of fluoride and deionized water enters as electrolyte
Row first time anodic oxidation, then anode is placed in deionized water and is ultrasonically treated removal nanoporous oxide layer；Then proceed to
Second of anodic oxidation reactions, anode is cleaned in deionized water afterwards, dry, be placed in Muffle furnace, the processing of oxygen atmosphere,
Cool to room temperature after end with the furnace, α-Fe are made2O3Nano-tube array；Wherein, first time anodic oxidation and second of anodic oxidation
Condition be 30-60V, 10-25 DEG C, oxidization time 1-10min；The condition handled in Muffle furnace is：200-500 DEG C, place
Manage time 1-2.5h；
(5) with α-Fe obtained above2O3Nano-tube array is working electrode, and platinized platinum is to be to electrode, saturated calomel electrode
Reference electrode, three-electrode electro Chemical system is formed, in graphene oxide dispersion, is deposited with cyclic voltammetry and reduces graphite
Alkene lamella is to α-Fe2O3In nano-tube array substrate, it is washed with deionized after terminating, nitrogen drying, obtained graphene/α-
Fe2O3Nano-tube array；Wherein, the condition of cyclic voltammetry deposition is -1.5~1.0V, sweep speed 30-60mV/a,
The scanning deposition number of turns is enclosed for 2-20；
(6) with graphene obtained above/α-Fe2O3Nano-tube array substrate is working electrode, and platinized platinum is to electrode, is satisfied
It is reference electrode with calomel electrode, forms three-electrode electro Chemical system, containing 1- ethyl-3-methylimidazole ethyl sulfonates
Copper salt solution in, with constant voltage method deposit Cu2O nano particles are to graphene/α-Fe2O3Nano-tube array substrate surface, sink
It is washed with deionized after the completion of product, nitrogen drying, Cu is made2O/ graphenes/α-Fe2O3Nano-tube array compound；Wherein,
The condition of constant voltage method deposition is：- 0.15~-0.3V, sedimentation time 500-4000s；
(7) organic dye waste water is removed the gred through grid after just precipitating, supernatant is pumped into equipped with compound adsorbent
In adsorption treatment pond, stirring and adsorbing handles 1-3h at 30 DEG C, then staticly settles, the supernatant after precipitation is pumped into reactor
In；
(8) Cu obtained above is added into reactor2O/ graphenes/α-Fe2O3Nano-tube array compound is as catalysis
Agent, and be pumped into air, the degradation treatment 10-16h under illumination condition, then stir process 4-6h in the dark state, last quiet
Precipitation is put, supernatant reaches discharge standard.
As the preferred of above-mentioned technical proposal, in step (1), the concentration of the graphite oxide dispersion is 0.5-
1.5mol/L。
As the preferred of above-mentioned technical proposal, in step (2), the porous carbon ball and cetyl trimethylammonium bromide
Mass ratio is 1：(0.001-0.005).
As the preferred of above-mentioned technical proposal, in step (3), graphite oxide dispersion, the quality for pre-processing porous carbon ball
Than for (15-33)：5.
As the preferred of above-mentioned technical proposal, in step (4), the fluoride is in ammonium fluoride, sodium fluoride, potassium fluoride
One or more mixing.
As the preferred of above-mentioned technical proposal, described in step (4) in electrolyte, the mass concentration of fluoride is 0.1-
0.4wt%, the volume fraction of deionized water is 0.5-4%.
As the preferred of above-mentioned technical proposal, in step (5), the concentration of the graphene oxide dispersion is 0.25-
2.0mg/ml。
As the preferred of above-mentioned technical proposal, in step (6), the mantoquita is copper sulphate, copper nitrate, copper chloride, acetic acid
One or more of mixing of copper；The concentration of copper salt solution is 0.005-0.04mol/L, wherein being 0.05- containing volume fraction
0.4% 1- ethyl-3-methylimidazole ethyl sulfonates.
As the preferred of above-mentioned technical proposal, in step (7), the dosage of the compound adsorbent is 0.5-3.5g/L.
As the preferred of above-mentioned technical proposal, in step (8), the dosage of the catalyst is 1-3g/L.
The invention has the advantages that：
The present invention prepares graphite oxide dispersion, dispersion liquid using supersound process first during preparing compound adsorbent
Middle graphite oxide is separated into relatively thin sheet distribution；Then it is of the invention by porous carbon ball cetyl trimethylammonium bromide
Ethanol solution processing, it is mixed with graphite oxide dispersion and handled at a certain temperature, the graphite oxide of sheet
Can effectively coated porous carbon ball, obtained compound adsorbent stability is good, and adsorption capacity is strong；
On the other hand, specific surface area of catalyst produced by the present invention is big, has good visible light-responded characteristic；And it can promote
The separation of entering light electron-hole pair, there is stronger redox ability；And the cost of material of catalyst produced by the present invention
Cheap, rich reserves, method is simple, and catalytic activity is high.
The present invention handles organic dye waste water using absorption method-photocatalytic degradation method, and effect is more preferable, and percent of decolourization is up to
100%, the clearance of total organic carbon is up to more than 95.5%.
Embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
The present invention is released, any restriction will not be formed to the present invention.
Embodiment 1
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, comprises the following steps：
(1) weigh graphite oxide to be added in deionized water, be ultrasonically treated 1h under 500W power, obtain graphite oxide and disperse
Liquid；Wherein, the concentration of the graphite oxide dispersion is 0.5mol/L；
(2) porous carbon ball is placed in the ethanol solution of cetyl trimethylammonium bromide, stirred at 30-40 DEG C
30min is handled, after processing terminates, filtering, obtained solid vacuum drying, pretreatment porous carbon ball is made；Wherein, it is described porous
The mass ratio of carbon ball and cetyl trimethylammonium bromide is 1：0.001；
(3) graphite oxide dispersion obtained above and pretreatment porous carbon ball are mixed and be transferred in three-necked flask, delayed
Slow to be warming up to 80-90 DEG C, reflow treatment 5h under 3000rpm, processing is cooled to room temperature after terminating, centrifugal treating is heavy after centrifugation
Shallow lake drying, obtains compound adsorbent；Wherein, graphite oxide dispersion, the mass ratio of pretreatment porous carbon ball are 15：5；
(4) high-purity iron plate is polished, then cleaned successively in absolute ethyl alcohol and distilled water, dried, it is standby；With above-mentioned place
High-purity iron plate after reason is negative electrode as anode, platinized platinum, and the ethylene glycol solution of fluoride and deionized water enters as electrolyte
Row first time anodic oxidation, then anode is placed in deionized water and is ultrasonically treated removal nanoporous oxide layer；Then proceed to
Second of anodic oxidation reactions, anode is cleaned in deionized water afterwards, dry, be placed in Muffle furnace, the processing of oxygen atmosphere,
Cool to room temperature after end with the furnace, α-Fe are made2O3Nano-tube array；Wherein, first time anodic oxidation and second of anodic oxidation
Condition be 30-60V, 10-25 DEG C, oxidization time 3min；The condition handled in Muffle furnace is：200 DEG C, processing time
1.5h；Wherein, the fluoride is ammonium fluoride；In the electrolyte, the mass concentration of fluoride is 0.15wt%, deionized water
Volume fraction be 1%；
(5) with α-Fe obtained above2O3Nano-tube array is working electrode, and platinized platinum is to be to electrode, saturated calomel electrode
Reference electrode, three-electrode electro Chemical system is formed, in graphene oxide dispersion, is deposited with cyclic voltammetry and reduces graphite
Alkene lamella is to α-Fe2O3In nano-tube array substrate, it is washed with deionized after terminating, nitrogen drying, obtained graphene/α-
Fe2O3Nano-tube array；Wherein, the condition of cyclic voltammetry deposition is -1.5~1.0V, sweep speed 30-60mV/a,
The scanning deposition number of turns is enclosed for 2-20；Wherein, the concentration of the graphene oxide dispersion is 0.3mg/ml；
(6) with graphene obtained above/α-Fe2O3Nano-tube array substrate is working electrode, and platinized platinum is to electrode, is satisfied
It is reference electrode with calomel electrode, forms three-electrode electro Chemical system, containing 1- ethyl-3-methylimidazole ethyl sulfonates
Copper salt solution in, with constant voltage method deposit Cu2O nano particles are to graphene/α-Fe2O3Nano-tube array substrate surface, sink
It is washed with deionized after the completion of product, nitrogen drying, Cu is made2O/ graphenes/α-Fe2O3Nano-tube array compound；Wherein,
The condition of constant voltage method deposition is：- 0.15~-0.3V, sedimentation time 500s；Wherein, the mantoquita is copper sulphate；Mantoquita
The concentration of the aqueous solution is 0.005mol/L, wherein containing the 1- ethyl-3-methylimidazole second that volume fraction is 0.05-0.4%
Base sulfonate；
(7) organic dye waste water is removed the gred through grid after just precipitating, supernatant is pumped into equipped with compound adsorbent
In adsorption treatment pond, stirring and adsorbing handles 1h at 30 DEG C, then staticly settles, the supernatant after precipitation is pumped into reactor；
Wherein, the dosage of the compound adsorbent is 0.5g/L；
(8) Cu obtained above is added into reactor2O/ graphenes/α-Fe2O3Nano-tube array compound is as catalysis
Agent, and be pumped into air, the degradation treatment 10h under illumination condition, then stir process 4h in the dark state, it is heavy finally to stand
Form sediment, supernatant reaches discharge standard；Wherein, the dosage of the catalyst is 1g/L.
Embodiment 2
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, comprises the following steps：
(1) weigh graphite oxide to be added in deionized water, be ultrasonically treated 1h under 500W power, obtain graphite oxide and disperse
Liquid；Wherein, the concentration of the graphite oxide dispersion is 1.5mol/L；
(2) porous carbon ball is placed in the ethanol solution of cetyl trimethylammonium bromide, stirred at 30-40 DEG C
70min is handled, after processing terminates, filtering, obtained solid vacuum drying, pretreatment porous carbon ball is made；Wherein, it is described porous
The mass ratio of carbon ball and cetyl trimethylammonium bromide is 1：0.005；
(3) graphite oxide dispersion obtained above and pretreatment porous carbon ball are mixed and be transferred in three-necked flask, delayed
Slow to be warming up to 80-90 DEG C, reflow treatment 5h under 3000rpm, processing is cooled to room temperature after terminating, centrifugal treating is heavy after centrifugation
Shallow lake drying, obtains compound adsorbent；Wherein, graphite oxide dispersion, the mass ratio of pretreatment porous carbon ball are 33：5；
(4) high-purity iron plate is polished, then cleaned successively in absolute ethyl alcohol and distilled water, dried, it is standby；With above-mentioned place
High-purity iron plate after reason is negative electrode as anode, platinized platinum, and the ethylene glycol solution of fluoride and deionized water enters as electrolyte
Row first time anodic oxidation, then anode is placed in deionized water and is ultrasonically treated removal nanoporous oxide layer；Then proceed to
Second of anodic oxidation reactions, anode is cleaned in deionized water afterwards, dry, be placed in Muffle furnace, the processing of oxygen atmosphere,
Cool to room temperature after end with the furnace, α-Fe are made2O3Nano-tube array；Wherein, first time anodic oxidation and second of anodic oxidation
Condition be 30-60V, 10-25 DEG C, oxidization time 5min；The condition handled in Muffle furnace is：500 DEG C, processing time
1h；Wherein, the fluoride is sodium fluoride；In the electrolyte, the mass concentration of fluoride is 0.25wt%, deionized water
Volume fraction is 1%；
(5) with α-Fe obtained above2O3Nano-tube array is working electrode, and platinized platinum is to be to electrode, saturated calomel electrode
Reference electrode, three-electrode electro Chemical system is formed, in graphene oxide dispersion, is deposited with cyclic voltammetry and reduces graphite
Alkene lamella is to α-Fe2O3In nano-tube array substrate, it is washed with deionized after terminating, nitrogen drying, obtained graphene/α-
Fe2O3Nano-tube array；Wherein, the condition of cyclic voltammetry deposition is -1.5~1.0V, sweep speed 30-60mV/a,
The scanning deposition number of turns is enclosed for 2-20；Wherein, the concentration of the graphene oxide dispersion is 0.35mg/ml；
(6) with graphene obtained above/α-Fe2O3Nano-tube array substrate is working electrode, and platinized platinum is to electrode, is satisfied
It is reference electrode with calomel electrode, forms three-electrode electro Chemical system, containing 1- ethyl-3-methylimidazole ethyl sulfonates
Copper salt solution in, with constant voltage method deposit Cu2O nano particles are to graphene/α-Fe2O3Nano-tube array substrate surface, sink
It is washed with deionized after the completion of product, nitrogen drying, Cu is made2O/ graphenes/α-Fe2O3Nano-tube array compound；Wherein,
The condition of constant voltage method deposition is：- 0.15~-0.3V, sedimentation time 4000s；Wherein, the mantoquita is copper acetate；Copper
The concentration of saline solution is 0.04mol/L, wherein containing the 1- ethyl-3-methylimidazole second that volume fraction is 0.05-0.4%
Base sulfonate；
(7) organic dye waste water is removed the gred through grid after just precipitating, supernatant is pumped into equipped with compound adsorbent
In adsorption treatment pond, stirring and adsorbing handles 3h at 30 DEG C, then staticly settles, the supernatant after precipitation is pumped into reactor；
Wherein, the dosage of the compound adsorbent is 3.5g/L；
(8) Cu obtained above is added into reactor2O/ graphenes/α-Fe2O3Nano-tube array compound is as catalysis
Agent, and be pumped into air, the degradation treatment 16h under illumination condition, then stir process 6h in the dark state, it is heavy finally to stand
Form sediment, supernatant reaches discharge standard；Wherein, the dosage of the catalyst is 3g/L.
Embodiment 3
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, comprises the following steps：
(1) weigh graphite oxide to be added in deionized water, be ultrasonically treated 1h under 500W power, obtain graphite oxide and disperse
Liquid；Wherein, the concentration of the graphite oxide dispersion is 1.0mol/L；
(2) porous carbon ball is placed in the ethanol solution of cetyl trimethylammonium bromide, stirred at 30-40 DEG C
40min is handled, after processing terminates, filtering, obtained solid vacuum drying, pretreatment porous carbon ball is made；Wherein, it is described porous
The mass ratio of carbon ball and cetyl trimethylammonium bromide is 1：0.002；
(3) graphite oxide dispersion obtained above and pretreatment porous carbon ball are mixed and be transferred in three-necked flask, delayed
Slow to be warming up to 80-90 DEG C, reflow treatment 5h under 3000rpm, processing is cooled to room temperature after terminating, centrifugal treating is heavy after centrifugation
Shallow lake drying, obtains compound adsorbent；Wherein, graphite oxide dispersion, the mass ratio of pretreatment porous carbon ball are 20：5；
(4) high-purity iron plate is polished, then cleaned successively in absolute ethyl alcohol and distilled water, dried, it is standby；With above-mentioned place
High-purity iron plate after reason is negative electrode as anode, platinized platinum, and the ethylene glycol solution of fluoride and deionized water enters as electrolyte
Row first time anodic oxidation, then anode is placed in deionized water and is ultrasonically treated removal nanoporous oxide layer；Then proceed to
Second of anodic oxidation reactions, anode is cleaned in deionized water afterwards, dry, be placed in Muffle furnace, the processing of oxygen atmosphere,
Cool to room temperature after end with the furnace, α-Fe are made2O3Nano-tube array；Wherein, first time anodic oxidation and second of anodic oxidation
Condition be 30-60V, 10-25 DEG C, oxidization time 5min；The condition handled in Muffle furnace is：230 DEG C, processing time
1.5h；Wherein, the fluoride is potassium fluoride；In the electrolyte, the mass concentration of fluoride is 0.25wt%, deionized water
Volume fraction be 2.5%；
(5) with α-Fe obtained above2O3Nano-tube array is working electrode, and platinized platinum is to be to electrode, saturated calomel electrode
Reference electrode, three-electrode electro Chemical system is formed, in graphene oxide dispersion, is deposited with cyclic voltammetry and reduces graphite
Alkene lamella is to α-Fe2O3In nano-tube array substrate, it is washed with deionized after terminating, nitrogen drying, obtained graphene/α-
Fe2O3Nano-tube array；Wherein, the condition of cyclic voltammetry deposition is -1.5~1.0V, sweep speed 30-60mV/a,
The scanning deposition number of turns is enclosed for 2-20；Wherein, the concentration of the graphene oxide dispersion is 0.5mg/ml；
(6) with graphene obtained above/α-Fe2O3Nano-tube array substrate is working electrode, and platinized platinum is to electrode, is satisfied
It is reference electrode with calomel electrode, forms three-electrode electro Chemical system, containing 1- ethyl-3-methylimidazole ethyl sulfonates
Copper salt solution in, with constant voltage method deposit Cu2O nano particles are to graphene/α-Fe2O3Nano-tube array substrate surface, sink
It is washed with deionized after the completion of product, nitrogen drying, Cu is made2O/ graphenes/α-Fe2O3Nano-tube array compound；Wherein,
The condition of constant voltage method deposition is：- 0.15~-0.3V, sedimentation time 1000s；Wherein, the mantoquita is copper sulphate；Copper
The concentration of saline solution is 0.01mol/L, wherein containing the 1- ethyl-3-methylimidazole second that volume fraction is 0.05-0.4%
Base sulfonate；
(7) organic dye waste water is removed the gred through grid after just precipitating, supernatant is pumped into equipped with compound adsorbent
In adsorption treatment pond, stirring and adsorbing handles 1.5h at 30 DEG C, then staticly settles, the supernatant after precipitation is pumped into reactor
In；Wherein, the dosage of the compound adsorbent is 1g/L；
(8) Cu obtained above is added into reactor2O/ graphenes/α-Fe2O3Nano-tube array compound is as catalysis
Agent, and be pumped into air, the degradation treatment 11h under illumination condition, then stir process 4.5h in the dark state, it is heavy finally to stand
Form sediment, supernatant reaches discharge standard；Wherein, the dosage of the catalyst is 1.5g/L.
Embodiment 4
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, comprises the following steps：
(1) weigh graphite oxide to be added in deionized water, be ultrasonically treated 1h under 500W power, obtain graphite oxide and disperse
Liquid；Wherein, the concentration of the graphite oxide dispersion is 1.1mol/L；
(2) porous carbon ball is placed in the ethanol solution of cetyl trimethylammonium bromide, stirred at 30-40 DEG C
50min is handled, after processing terminates, filtering, obtained solid vacuum drying, pretreatment porous carbon ball is made；Wherein, it is described porous
The mass ratio of carbon ball and cetyl trimethylammonium bromide is 1：0.003；
(3) graphite oxide dispersion obtained above and pretreatment porous carbon ball are mixed and be transferred in three-necked flask, delayed
Slow to be warming up to 80-90 DEG C, reflow treatment 5h under 3000rpm, processing is cooled to room temperature after terminating, centrifugal treating is heavy after centrifugation
Shallow lake drying, obtains compound adsorbent；Wherein, graphite oxide dispersion, the mass ratio of pretreatment porous carbon ball are 21：5；
(4) high-purity iron plate is polished, then cleaned successively in absolute ethyl alcohol and distilled water, dried, it is standby；With above-mentioned place
High-purity iron plate after reason is negative electrode as anode, platinized platinum, and the ethylene glycol solution of fluoride and deionized water enters as electrolyte
Row first time anodic oxidation, then anode is placed in deionized water and is ultrasonically treated removal nanoporous oxide layer；Then proceed to
Second of anodic oxidation reactions, anode is cleaned in deionized water afterwards, dry, be placed in Muffle furnace, the processing of oxygen atmosphere,
Cool to room temperature after end with the furnace, α-Fe are made2O3Nano-tube array；Wherein, first time anodic oxidation and second of anodic oxidation
Condition be 30-60V, 10-25 DEG C, oxidization time 6min；The condition handled in Muffle furnace is：260 DEG C, processing time
2h；Wherein, the fluoride is one or more of mixing in ammonium fluoride, sodium fluoride, potassium fluoride；In the electrolyte, fluorination
The mass concentration of thing is 0.35wt%, and the volume fraction of deionized water is 3%；
(5) with α-Fe obtained above2O3Nano-tube array is working electrode, and platinized platinum is to be to electrode, saturated calomel electrode
Reference electrode, three-electrode electro Chemical system is formed, in graphene oxide dispersion, is deposited with cyclic voltammetry and reduces graphite
Alkene lamella is to α-Fe2O3In nano-tube array substrate, it is washed with deionized after terminating, nitrogen drying, obtained graphene/α-
Fe2O3Nano-tube array；Wherein, the condition of cyclic voltammetry deposition is -1.5~1.0V, sweep speed 30-60mV/a,
The scanning deposition number of turns is enclosed for 2-20；Wherein, the concentration of the graphene oxide dispersion is 1.0mg/ml；
(6) with graphene obtained above/α-Fe2O3Nano-tube array substrate is working electrode, and platinized platinum is to electrode, is satisfied
It is reference electrode with calomel electrode, forms three-electrode electro Chemical system, containing 1- ethyl-3-methylimidazole ethyl sulfonates
Copper salt solution in, with constant voltage method deposit Cu2O nano particles are to graphene/α-Fe2O3Nano-tube array substrate surface, sink
It is washed with deionized after the completion of product, nitrogen drying, Cu is made2O/ graphenes/α-Fe2O3Nano-tube array compound；Wherein,
The condition of constant voltage method deposition is：- 0.15~-0.3V, sedimentation time 2000s；Wherein, the mantoquita is copper sulphate, nitre
One or more of mixing of sour copper, copper chloride, copper acetate；The concentration of copper salt solution is 0.02mol/L, wherein containing volume integral
Number is 0.2% 1- ethyl-3-methylimidazole ethyl sulfonates；
(7) organic dye waste water is removed the gred through grid after just precipitating, supernatant is pumped into equipped with compound adsorbent
In adsorption treatment pond, stirring and adsorbing handles 2h at 30 DEG C, then staticly settles, the supernatant after precipitation is pumped into reactor；
Wherein, the dosage of the compound adsorbent is 1.5g/L；
(8) Cu obtained above is added into reactor2O/ graphenes/α-Fe2O3Nano-tube array compound is as catalysis
Agent, and be pumped into air, the degradation treatment 13h under illumination condition, then stir process 5h in the dark state, it is heavy finally to stand
Form sediment, supernatant reaches discharge standard；Wherein, the dosage of the catalyst is 2g/L.
Embodiment 5
A kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, comprises the following steps：
(1) weigh graphite oxide to be added in deionized water, be ultrasonically treated 1h under 500W power, obtain graphite oxide and disperse
Liquid；Wherein, the concentration of the graphite oxide dispersion is 1.3mol/L；
(2) porous carbon ball is placed in the ethanol solution of cetyl trimethylammonium bromide, stirred at 30-40 DEG C
60min is handled, after processing terminates, filtering, obtained solid vacuum drying, pretreatment porous carbon ball is made；Wherein, it is described porous
The mass ratio of carbon ball and cetyl trimethylammonium bromide is 1：0.004；
(3) graphite oxide dispersion obtained above and pretreatment porous carbon ball are mixed and be transferred in three-necked flask, delayed
Slow to be warming up to 80-90 DEG C, reflow treatment 5h under 3000rpm, processing is cooled to room temperature after terminating, centrifugal treating is heavy after centrifugation
Shallow lake drying, obtains compound adsorbent；Wherein, graphite oxide dispersion, the mass ratio of pretreatment porous carbon ball are 31：5；
(4) high-purity iron plate is polished, then cleaned successively in absolute ethyl alcohol and distilled water, dried, it is standby；With above-mentioned place
High-purity iron plate after reason is negative electrode as anode, platinized platinum, and the ethylene glycol solution of fluoride and deionized water enters as electrolyte
Row first time anodic oxidation, then anode is placed in deionized water and is ultrasonically treated removal nanoporous oxide layer；Then proceed to
Second of anodic oxidation reactions, anode is cleaned in deionized water afterwards, dry, be placed in Muffle furnace, the processing of oxygen atmosphere,
Cool to room temperature after end with the furnace, α-Fe are made2O3Nano-tube array；Wherein, first time anodic oxidation and second of anodic oxidation
Condition be 30-60V, 10-25 DEG C, oxidization time 7min；The condition handled in Muffle furnace is：400 DEG C, processing time
2h；Wherein, the fluoride is potassium fluoride；In the electrolyte, the mass concentration of fluoride is 0.35wt%, deionized water
Volume fraction is 3.5%；
(5) with α-Fe obtained above2O3Nano-tube array is working electrode, and platinized platinum is to be to electrode, saturated calomel electrode
Reference electrode, three-electrode electro Chemical system is formed, in graphene oxide dispersion, is deposited with cyclic voltammetry and reduces graphite
Alkene lamella is to α-Fe2O3In nano-tube array substrate, it is washed with deionized after terminating, nitrogen drying, obtained graphene/α-
Fe2O3Nano-tube array；Wherein, the condition of cyclic voltammetry deposition is -1.5~1.0V, sweep speed 30-60mV/a,
The scanning deposition number of turns is enclosed for 2-20；Wherein, the concentration of the graphene oxide dispersion is 1.5mg/ml；
(6) with graphene obtained above/α-Fe2O3Nano-tube array substrate is working electrode, and platinized platinum is to electrode, is satisfied
It is reference electrode with calomel electrode, forms three-electrode electro Chemical system, containing 1- ethyl-3-methylimidazole ethyl sulfonates
Copper salt solution in, with constant voltage method deposit Cu2O nano particles are to graphene/α-Fe2O3Nano-tube array substrate surface, sink
It is washed with deionized after the completion of product, nitrogen drying, Cu is made2O/ graphenes/α-Fe2O3Nano-tube array compound；Wherein,
The condition of constant voltage method deposition is：- 0.15~-0.3V, sedimentation time 3000s；Wherein, the mantoquita is copper chloride；Copper
The concentration of saline solution is 0.03mol/L, wherein containing the 1- ethyl-3-methylimidazole second that volume fraction is 0.05-0.4%
Base sulfonate；
(7) organic dye waste water is removed the gred through grid after just precipitating, supernatant is pumped into equipped with compound adsorbent
In adsorption treatment pond, stirring and adsorbing handles 2.5h at 30 DEG C, then staticly settles, the supernatant after precipitation is pumped into reactor
In；Wherein, the dosage of the compound adsorbent is 3.3g/L；
(8) Cu obtained above is added into reactor2O/ graphenes/α-Fe2O3Nano-tube array compound is as catalysis
Agent, and be pumped into air, the degradation treatment 15h under illumination condition, then stir process 5.5h in the dark state, it is heavy finally to stand
Form sediment, supernatant reaches discharge standard；Wherein, the dosage of the catalyst is 2g/L.
The concentration for the organic dye waste water that the present invention is handled is 300-700mg/L, and the clearance of total organic carbon is 95.5%
More than, percent of decolourization is up to 100%.
Claims (10)
1. the method for a kind of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water, it is characterised in that including following step
Suddenly：
(1) weigh graphite oxide to be added in deionized water, be ultrasonically treated 1h under 500W power, obtain graphite oxide dispersion；
(2) porous carbon ball is placed in the ethanol solution of cetyl trimethylammonium bromide, the stir process at 30-40 DEG C
30-70min, after processing terminates, filtering, obtained solid vacuum drying, pretreatment porous carbon ball is made；
(3) graphite oxide dispersion obtained above and pretreatment porous carbon ball are mixed and be transferred in three-necked flask, slowly risen
Temperature is to 80-90 DEG C, and reflow treatment 5h under 3000rpm, processing is cooled to room temperature, centrifugal treating after terminating, the precipitation after centrifugation is done
It is dry, obtain compound adsorbent；
(4) high-purity iron plate is polished, then cleaned successively in absolute ethyl alcohol and distilled water, dried, it is standby；After above-mentioned processing
High-purity iron plate as anode, platinized platinum be negative electrode, the ethylene glycol solution of fluoride and deionized water carries out the as electrolyte
Anodic oxidation, then anode is placed in deionized water and is ultrasonically treated removal nanoporous oxide layer；Then proceed to second
Secondary anodic oxidation reactionses, anode is cleaned in deionized water afterwards, dry, be placed in Muffle furnace, the processing of oxygen atmosphere, terminated
After cool to room temperature with the furnace, α-Fe are made2O3Nano-tube array；Wherein, the bar of first time anodic oxidation and second of anodic oxidation
Part is 30-60V, 10-25 DEG C, oxidization time 1-10min；The condition handled in Muffle furnace is：200-500 DEG C, during processing
Between 1-2.5h；
(5) with α-Fe obtained above2O3Nano-tube array is working electrode, and platinized platinum is that saturated calomel electrode is reference to electrode
Electrode, three-electrode electro Chemical system is formed, in graphene oxide dispersion, with cyclic voltammetry deposition and reduced graphene piece
Layer arrives α-Fe2O3In nano-tube array substrate, it is washed with deionized after terminating, nitrogen drying, graphene/α-Fe is made2O3Receive
Mitron array；Wherein, the condition of the cyclic voltammetry deposition is -1.5~1.0V, sweep speed 30-60mV/a, and scanning is heavy
The product number of turns is enclosed for 2-20；
(6) with graphene obtained above/α-Fe2O3Nano-tube array substrate is working electrode, and platinized platinum is sweet to electrode, saturation
Mercury electrode is reference electrode, three-electrode electro Chemical system is formed, in the copper containing 1- ethyl-3-methylimidazole ethyl sulfonates
In saline solution, Cu is deposited with constant voltage method2O nano particles are to graphene/α-Fe2O3Nano-tube array substrate surface, has been deposited
It is washed with deionized after, nitrogen drying, Cu is made2O/ graphenes/α-Fe2O3Nano-tube array compound；Wherein, it is described
Constant voltage method deposition condition be：- 0.15~-0.3V, sedimentation time 500-4000s；
(7) organic dye waste water is removed the gred through grid after just precipitating, supernatant is pumped into the absorption equipped with compound adsorbent
In processing pond, stirring and adsorbing handles 1-3h at 30 DEG C, then staticly settles, the supernatant after precipitation is pumped into reactor；
(8) Cu obtained above is added into reactor2O/ graphenes/α-Fe2O3Nano-tube array compound as catalyst,
And air is pumped into, the degradation treatment 10-16h under illumination condition, then stir process 4-6h in the dark state, it is heavy finally to stand
Form sediment, supernatant reaches discharge standard.
2. a kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as claimed in claim 1, it is special
Sign is：In step (1), the concentration of the graphite oxide dispersion is 0.5-1.5mol/L.
3. a kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as claimed in claim 1, it is special
Sign is：In step (2), the mass ratio of the porous carbon ball and cetyl trimethylammonium bromide is 1：(0.001-0.005).
4. a kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as claimed in claim 1, it is special
Sign is：In step (3), graphite oxide dispersion, the mass ratio of pretreatment porous carbon ball are (15-33)：5.
5. a kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as claimed in claim 1, it is special
Sign is：In step (4), the fluoride is one or more of mixing in ammonium fluoride, sodium fluoride, potassium fluoride.
6. a kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as claimed in claim 1, it is special
Sign is：Described in step (4) in electrolyte, the mass concentration of fluoride is 0.1-0.4wt%, the volume fraction of deionized water
For 0.5-4%.
7. a kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as claimed in claim 1, it is special
Sign is：In step (5), the concentration of the graphene oxide dispersion is 0.25-2.0mg/ml.
8. a kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as claimed in claim 1, it is special
Sign is：In step (6), the mantoquita is one or more of mixing of copper sulphate, copper nitrate, copper chloride, copper acetate；Mantoquita water
The concentration of solution is 0.005-0.04mol/L, wherein containing the 1- ethyl-3-methylimidazoles that volume fraction is 0.05-0.4%
Ethyl sulfonate.
9. a kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as claimed in claim 1, it is special
Sign is：In step (7), the dosage of the compound adsorbent is 0.5-3.5g/L.
10. a kind of method of absorption method-photocatalytic degradation method Combined Treatment organic dye waste water as claimed in claim 1, its
It is characterised by：In step (8), the dosage of the catalyst is 1-3g/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109250849A (en) * | 2018-09-22 | 2019-01-22 | 福建凤竹纺织科技股份有限公司 | A kind of processing method of textile waste |
| CN113651471A (en) * | 2021-09-07 | 2021-11-16 | 福泉兴盛生物科技有限公司 | Efficient treatment method for organic wastewater |
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2017
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109250849A (en) * | 2018-09-22 | 2019-01-22 | 福建凤竹纺织科技股份有限公司 | A kind of processing method of textile waste |
| CN109250849B (en) * | 2018-09-22 | 2021-08-27 | 福建凤竹纺织科技股份有限公司 | Treatment method of textile wastewater |
| CN113651471A (en) * | 2021-09-07 | 2021-11-16 | 福泉兴盛生物科技有限公司 | Efficient treatment method for organic wastewater |
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