CN110369151A - A kind of method of nanometer of collecting agent ion flotation processing heavy metal wastewater thereby - Google Patents
A kind of method of nanometer of collecting agent ion flotation processing heavy metal wastewater thereby Download PDFInfo
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- CN110369151A CN110369151A CN201910620670.6A CN201910620670A CN110369151A CN 110369151 A CN110369151 A CN 110369151A CN 201910620670 A CN201910620670 A CN 201910620670A CN 110369151 A CN110369151 A CN 110369151A
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- heavy metal
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- collecting agent
- ion
- flotation
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- 238000005188 flotation Methods 0.000 title claims abstract description 53
- 239000002351 wastewater Substances 0.000 title claims abstract description 36
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000003350 kerosene Substances 0.000 claims abstract description 12
- 239000004088 foaming agent Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 238000005273 aeration Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims 1
- 235000011613 Pinus brutia Nutrition 0.000 claims 1
- 241000018646 Pinus brutia Species 0.000 claims 1
- 239000006071 cream Substances 0.000 claims 1
- 238000004945 emulsification Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000010842 industrial wastewater Substances 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 239000010802 sludge Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 230000002045 lasting effect Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 34
- 239000000243 solution Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 238000005189 flocculation Methods 0.000 description 5
- 230000016615 flocculation Effects 0.000 description 5
- 239000011133 lead Substances 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WAKHLWOJMHVUJC-SQFISAMPSA-N (2z)-2-hydroxyimino-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(=N/O)/C(O)C1=CC=CC=C1 WAKHLWOJMHVUJC-SQFISAMPSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- KTEXACXVPZFITO-UHFFFAOYSA-N molybdenum uranium Chemical compound [Mo].[U] KTEXACXVPZFITO-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical group [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/002—Inorganic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
-
- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/008—Water purification, e.g. for process water recycling
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physical Water Treatments (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses the methods of a kind of nanometer of collecting agent ion flotation processing heavy metal wastewater thereby, this method comprises the following steps: a certain amount of graphene oxide solution is added as ion flotation nanometer collecting agent in the flotation cell of the waste water (pH 4-8) of Xiang Hanyou heavy metal, is stirred to react；Then, a certain amount of emulsified kerosene is added as flocculant, lasting stirring；Then, it is foaming agent that a certain amount of terpenic oil, which is added, and continues to stir；Finally, inflation, under hydrophobic forces, carried metal pollutant graphene oxide is adhered on bubble, and is floated and be gathered in the froth bed spilling on liquid level upper layer, realizes the removal of heavy metal ion and the purification of water.Processed waste water reaches National Industrial wastewater discharge standard.This method is easy to operate, occupied area is small, low energy consumption, concentration ratio is high, sludge quantity is few, has certain industrial value and social benefit.
Description
Technical field
The invention belongs to mineral manufacture fields, and in particular to a kind of nanometer of collecting agent ion flotation handles heavy metal wastewater thereby
Method.
Background technique
The research of ion floatation method processing sewage containing heavy metal ion has been reported.For example, Han Guihong etc. is in a kind of " chelating
In type metal ion floating agent, preparation method and its application method " (CN106238010A), with cyclodextrin, sodium hydride and
Succinic anhydride has synthesized a kind of chelating type metal ion floating agent through two-step method for raw material, is applied to metal ion flotation, right
Metal ion shows good removal effect.Sun Yajie is in " a kind of flocfloatation equipment of sewage treatment "
(CN205892794U) in, flotation column is increased in flocfloatation equipment, touches the formation of bubble, bubble with flocculation group
To hit, contact be in the eddy flow of rule, is completed under current intelligence, is especially delivered to wastewater fluids layer on the inside of antipriming pipe and passes through
The air that the hole of antipriming pipe enters meets, and rigid incipient air is cut into countless minute bubbles by the sewage of eddy flow, stingy
Bubble collides to form combination, and floats up to the top of flotation cell with particle, flocculation group.It is greatly improved the flotation of floc sedimentation
Efficiency.Imperial prestige etc. is in " a kind of technique and device of pressure dissolved air floatation method removal heavy metal ions in sewage "
(CN104118951A) in, waste water will be first passed through to calcium hydroxide first makes it neutralize the acid ion in waste water, then is passed through oil
Sour sodium makes the sediment hydrophobization to be formed, and then makes particle flocculation；Microbubble is generated using pressure air-dissolving method, will be generated after pressurization
Saturated dissolved gas water carry out flotation by being discharged into flocculation sewage；Finally the dross floatingly selected is collected and handled.It should
Technique category pressure dissolved air floatation purification process, concise in technology operate convenient, continuously-running.In addition, E. A. Jdid etc. is with α-
Benzoin oxime is collecting agent, using ion flotation technology from the sulphuric leachate of uranium-bearing Selective Separation molybdenum, can will
The molybdenum uranium ratio of Benlomond leachate drops to 0.09 from 0.50, while obtaining the molybdenum concentrate containing Mo about 15%.Meng Youting etc.
It has studied with the Cu in Tea Saponin removal waste water2+、Pb2+And Cd2+, highest removal rate respectively reached 81.13%, 96.03% and
71.17%, and removal process has stronger selectivity.Fu Yan is elementary to make collecting agent with cetyl trimethylammonium bromide, with from
Sub- floatation carries out flotation decolorization to reactive dyed wastewater, and percent of decolourization is up to 80%~90%, processed waste water coloration
Reach national emission standard, and dross amount is few.For Hu et al. with nano silica (SNPs) for collecting agent, flotation removes waste water
In methylene blue, when SNPs concentration is 600mg/L, the removal rate of methylene blue is up to nearly 95%, and SNPs is at least recyclable
It utilizes 5 times.Ion floatation method is formed because having many advantages, such as that flexible operation is easy, occupied area is small, sludge quantity is few and concentration ratio is high
For a kind of effective ways for handling heavy metal wastewater thereby.Collecting agent performance has been approved ion flotation with great influence, and
Domestic and international researcher is reducing collector dosage, is increasing acquisition performance, raising collecting agent power of regeneration and biological collectors application
Etc. carried out a large amount of fruitful research work.
Graphene oxide (GO) is a kind of two-dimensional carbon nanomaterial, has that large specific surface area, chemical activity be strong, biofacies
The features such as capacitive is good and large amount of adsorption.Similar with the amphipathic composition of conventional surfactants, a large amount of hydroxyl is not only contained on the surface GO
The hydrophilic oxygen-containing functional group such as base, carboxyl can pass through a large amount of heavy metal ion of complex reaction quick adsorption；And there are parts
The unoxidized pi-conjugated sp of π-2Structural domain, have the hydrophobicity similar with natural graphite, can under hydrophobic forces with nonpolarity
Suction-operated occurs for substance or bubble.It follows that GO has one as ion flotation nanometer collecting agent processing heavy metal wastewater thereby
Fixed feasibility and application potential.However, up to now, about GO as nanometer collecting agent ion flotation purification of heavy metal waste water
Research there is not been reported.
Summary of the invention
The present invention is directed to big, at high cost, the possible secondary pollution of current ion flotation collector dosage and heavy metal ion is gone
The problems such as low except rate, the method for proposing a kind of nanometer of collecting agent ion flotation processing heavy metal wastewater thereby.
Based on above-mentioned purpose, the technical solution adopted by the present invention is as follows:
The method of a kind of nanometer of collecting agent ion flotation processing heavy metal wastewater thereby, using graphene oxide solution as ion flotation nanometer
Collecting agent.Firstly, a certain amount of graphene oxide solution is added into the flotation cell containing heavy metal wastewater thereby, it is stirred, such as
Shown in Fig. 1, the hydroxyl and carboxyl on the surface nanometer collecting agent graphite oxide (GO) adsorb fixed heavy metal ion by complex reaction；
Then, a certain amount of emulsified kerosene is added as flocculant, is stirred, the nanometer collecting agent (M- after making adsorbing metal ions
GO) particle flocculation grows into large-sized wadding body；Then, it is foaming agent that a certain amount of terpenic oil, which is added, and is stirred；Most
Afterwards, it inflates, under hydrophobic forces, wadding body is adhered on bubble by the graphitized area of M-GO unoxidized surface makes bubble
Mineralising, and then float and be gathered in the froth bed spilling on liquid level upper layer, realize the removal of heavy metal ions in wastewater and the purification of water.
Handled heavy metal wastewater thereby contains one or more of Cu, Pb, Zn, Hg, Co and Ni metal ion, gold
Category ion concentration is 10-2000 ppm, wastewater pH 4-8.
The C/O atomic ratio of nanometer collecting agent graphene oxide used can be 1.5-4.0, and single layer number content can be 30%
More than, the concentration for controlling graphene oxide in mixed liquor is 0.5-2.0 mg/L.
The granularity D90 of emulsified kerosene used is 0.1-2.5 μm, additional amount 20-100mg/L.
The additional amount of foaming agent terpenic oil used is 10-30mg/L.
Ion flotation device used is XFD II agitation impeller flotator, and flotation sump volume is 250 mL, and aeration quantity is
0.6-1.5L/min, flotation time are 5-10min.
The present invention is floating using ion using the graphene oxide similar with the amphipathic component of surfactant as nanometer collecting agent
Processing is published to be up to containing effluent containing heavy metal ions, significant effect, removal of heavy metal ions rates such as Cu, Pb, Zn, Hg, Co and Ni
95%, the turbidity of processed waste water is in 3.9NTU hereinafter, reaching industrial wastewater discharge standard.This method is easy to operate, occupied area
It is small, low energy consumption, concentration ratio is high, sludge quantity is few, being carried out industrial applications has certain industrial value and social benefit.
Detailed description of the invention
Fig. 1 is the working principle diagram of present invention removal heavy metal ions in wastewater；
Fig. 2 is Cu2+The relational graph of removal rate and tail washings turbidity and foaming agent concentration.
Specific embodiment
Technical solution of the present invention is described in further detail combined with specific embodiments below, but protection model of the invention
It encloses and is not limited thereto.
Graphene oxide in following embodiments is prepared using Hummers method, and detailed step is as follows:
(1) it measures the commercially available concentrated sulfuric acid of 230 mL to be placed in ice bath in dry conical flask, and by conical flask, with 400 rev/
10 min of min revolving speed magnetic agitation；
(2) 10.0 g natural graphite powders and 5.0 g sodium nitrate are mixed and is added in conical flask, and continue to stir 10 min, make it
It is uniformly mixed；
(3) it weighs 30.0 g potassium permanganate to be slowly added into conical flask, the temperature for controlling ice bath is no more than 10 DEG C, continues
Stir 1 h；Later, the conical flask equipped with mixed liquor is transferred in 38 ± 1 DEG C of tepidarium, and continues to stir 2 h；
(4) 460 mL deionized waters are added dropwise into conical flask, and bath temperature is risen to 95 DEG C, are kept stirring 0.5 h；
(5) after pyroreaction, 1400 mL, the above-mentioned mixed liquor of 40 DEG C of deionized water dilution is added, add later
About 50 mL H2O2Solution (30v%) is until bubble-free in mixed liquor generates；
(6) mixed liquor is centrifuged 20 min under the centrifugal acceleration of 1720 × g, after pouring out upper liquid, lower sediment is distinguished again
It is repeatedly washed with the dilute hydrochloric acid of 5wt% and 40 DEG C of deionized waters, until upper liquid pH value reaches 6.5 or so after centrifugation, and is free of
SO4 2-Until.
(7) precipitating after cleaning is put into vacuum freezing drying oven dry 48 h to get graphite oxide product.
The detailed preparation step of graphene oxide solution is as follows:
(1) a certain amount of graphite oxide powder is weighed, the deionized water of certain volume is added, is existed with high-shearing dispersion emulsifying machine
3 min of high-speed stirred, makes it be dispersed into uniform suspension under 10000 rev/min revolving speeds, and the concentration for controlling graphite oxide is
5.0 mg/mL；
(2) by the suspension ultrasonic cell disruption instrument in (1), ultrasound removes 10 min under conditions of amplitude is 40%, i.e.,
Obtain graphene oxide solution.
Ion flotation device used is XFD II agitation impeller flotator in following embodiments, and flotation sump volume is 250
mL。
Embodiment 1:
The method of lead ion in a kind of nanometer of collecting agent ion flotation processing heavy metal wastewater thereby, detailed process is as follows:
The lead ion solution that 250mL concentration is 10ppm is added in the ion flotation device that flotation cell is 250mL, solution is adjusted
PH is 4.0, and a certain amount of graphene oxide is added as nanometer collecting agent, controls the concentration of graphene oxide in mixed solution
For 0.5mg/L, 5min is stirred with 1800rpm revolving speed；Then, the flocculant emulsified kerosene that D90 is 0.1 μm, emulsified kerosene is added
Additional amount is 20mg/L, persistently stirs 3min；Then, foaming agent terpenic oil is added according to 10mg/L, continues to stir 3min；Most
Afterwards, the flotation 5min in the case where aeration quantity is 0.6L/min, the turbidity for measuring tail washings is 3.9 NTU, and the remnants of lead ion are dense in tail washings
Degree is 0.2mg/L, has reached the discharge standard of industrial wastewater.
Embodiment 2:
The method of copper ion in a kind of nanometer of collecting agent ion flotation processing heavy metal wastewater thereby, detailed process is as follows:
The copper ion solution that 250mL concentration is 500ppm is added in the ion flotation device that flotation cell is 250mL, solution is adjusted
PH is 6.5, and a certain amount of graphene oxide is added as nanometer collecting agent, controls the concentration of graphene oxide in mixed solution
For 1.0mg/L, 5min is stirred with 1800rpm revolving speed；Then, the flocculant emulsified kerosene that D90 is 2.0 μm, emulsified kerosene is added
Additional amount is 100mg/L, persistently stirs 3min；Then, foaming agent terpenic oil is added according to the additional amount of 15mg/L, continues to stir
3min；Finally, the flotation 7min in the case where aeration quantity is 1.1L/min, the turbidity for measuring tail washings is 2.2 NTU, copper ion in tail washings
Residual concentration is 0.8mg/L, has reached the discharge standard of industrial wastewater.
In the case where other conditions are constant, only change the additional amount of terpenic oil, the additional amount of terpenic oil removes copper ion
It is processed into and the influence of turbidity is specifically detailed in Fig. 2, as shown in Figure 2, in the range of 10g/L ~ 30g/L, the addition of terpenic oil
The influence measured to copper ion removal rate is little, and with the increase of terpenic oil additional amount, the turbidity of solution reduces.
Embodiment 3:
The method of zinc ion in a kind of nanometer of collecting agent ion flotation processing heavy metal wastewater thereby, detailed process is as follows:
The zinc ion solution that 250mL concentration is 2000ppm is added in the ion flotation device that flotation cell is 250mL, is adjusted molten
Liquid pH is 7.0, and a certain amount of graphene oxide is added as nanometer collecting agent, and graphene oxide is dense in control mixed solution
Degree is 2.0mg/L, stirs 5min with 1800rpm revolving speed；Then, the flocculant emulsified kerosene that D90 is 0.1 μm is added, emulsifies coal
Oily additional amount is 20mg/L, persistently stirs 3min；Then, foaming agent terpenic oil is added according to the additional amount of 25mg/L, continues to stir
Mix 3min；Finally, the flotation 10min in the case where aeration quantity is 1.5L/min, the turbidity for measuring tail washings is 1.3NTU, zinc ion in tail washings
Residual concentration be 0.4mg/L, reached the discharge standard of industrial wastewater.
Embodiment 4:
The method of copper, lead, zinc ion in a kind of nanometer of collecting agent ion flotation processing heavy metal wastewater thereby, detailed process is as follows:
It is 250mL that flotation cell, which is added, in the solution that 250mL copper, lead, zinc ion concentration are respectively 80ppm, 150ppm and 200ppm
Ion flotation device in, adjusting pH value of solution is 8.0, and a certain amount of graphene oxide is added as nanometer collecting agent, is controlled
The concentration of graphene oxide is 1.2mg/L in mixed solution, stirs 5min with 1800rpm revolving speed；Then, it is 0.4 μm that D90, which is added,
Flocculant emulsified kerosene, emulsified kerosene additional amount be 50mg/L, persistently stir 3min；Then, according to the additional amount of 20mg/L
Foaming agent terpenic oil is added, continues to stir 3min；Finally, the flotation 8min in the case where aeration quantity is 1.3L/min, measures flotation tail washings
Turbidity be 1.3NTU, copper, lead, zinc ion concentration reduce most 0.5ppm, 0.4ppm and 0.7ppm respectively in tail washings, reach
The discharge standard of industrial wastewater.
Claims (6)
1. the method for a kind of nanometer of collecting agent ion flotation processing heavy metal wastewater thereby, which comprises the steps of: Xiang Han
There is the waste water of heavy metal that a certain amount of graphene oxide is added as ion flotation nanometer collecting agent, stirs evenly；Then, emulsification is added
Kerosene is stirred evenly as flocculant；Then, terpenic oil is added as foaming agent, stirs evenly；Finally, carrying out flotation under Aerated stirring, i.e.,
?.
2. the method for according to claim 1 nanometer of collecting agent ion flotation processing heavy metal wastewater thereby, which is characterized in that institute
The heavy metal wastewater thereby of processing contains one or more of Cu, Pb, Zn, Hg, Co and Ni metal ion, metal ion it is dense
Degree is 10-2000 ppm, wastewater pH 4-8.
3. the method for according to claim 1 nanometer of collecting agent ion flotation processing heavy metal wastewater thereby, which is characterized in that institute
It can be 1.5-4.0 with the C/O atomic ratio of nanometer collecting agent graphene oxide, single layer number content can be 30% or more, and control is mixed
The concentration for closing graphene oxide in liquid is 0.5-2.0 mg/L.
4. the method for according to claim 1 nanometer of collecting agent ion flotation processing heavy metal wastewater thereby, which is characterized in that cream
The granularity D90 for changing kerosene is 0.1-2.5 μm, and additional amount is 20-100mg/L.
5. the method for according to claim 1 nanometer of collecting agent ion flotation processing heavy metal wastewater thereby, which is characterized in that pine
The additional amount of alcohol oil is 10-30mg/L.
6. the method for according to claim 1 nanometer of collecting agent ion flotation processing heavy metal wastewater thereby, which is characterized in that fill
Aeration quantity is 0.6-1.5L/min when gas agitating, and flotation time is 5-10min.
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