CN106219685B - It is a kind of to remove Cr in water removal using different complexing agent assisted electrochemicals3+Method - Google Patents
It is a kind of to remove Cr in water removal using different complexing agent assisted electrochemicals3+Method Download PDFInfo
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- CN106219685B CN106219685B CN201610810307.7A CN201610810307A CN106219685B CN 106219685 B CN106219685 B CN 106219685B CN 201610810307 A CN201610810307 A CN 201610810307A CN 106219685 B CN106219685 B CN 106219685B
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
Cr in water removal is removed using different complexing agent assisted electrochemicals the present invention relates to a kind of3+Method.Cr will be contained3+Waste water is introduced into reaction chamber, a certain amount of complexing agent and supporting electrolyte sodium sulphate is added, using the stainless steel mesh sheet that single-walled carbon nanotube is modified as cathode, titanium net is anode, adjusting reaction chamber pH is certain value, with certain current density, energization is handled after a certain period of time, with spectrophotometer measurement and calculates Cr3+Removal rate, obtain can qualified discharge waste water.The present invention, which includes 1, addition different type complexing agent, can change Cr3+Form in aqueous solution makes it easier to remove.2, Cr is being improved3+Energy consumption of reaction is reduced while removal rate.
Description
Technical field
This patent is related to a kind of technical field of waste water processing, and in particular to a kind of to be gone using different complexing agent assisted electrochemicals
Except trivalent chromium (Cr in waste water3+) method.
Background technique
Chromium is widely used in plating, intermetallic composite coating, pigment, leather processing, chemicals manufacture, electronic equipment and catalysis
The industries such as industry have a large amount of Cr daily in all conglomeraties6+And Cr3+Acid waste water generates.As people are to Cr6+Toxicity recognize
Know, Cr6+Use obtained stringent control, and Cr in chromate waste water3+Still largely exist and proportion becomes in increase
Gesture.Although Cr3+Toxicity be not so good as Cr6+Strongly, but in the natural environment, there are Cr6+And Cr3+Mutual conversion phenomena, Cr3+It is right
The mankind and natural environment have great potential threat, and it is therefore necessary to a large amount of Cr3+Waste water is handled.
Currently, Cr in aqueous solution3+Removing method mainly include absorption, electric flocculation, UF membrane, hydroxide precipitation method
Deng, but all there are some the shortcomings that not can avoid.Absorption method is slow in the presence of absorption pollutant speed, and adsorption capacity is smaller and vulnerable to ring
The problems such as border factor influences；The problems such as that there are power consumption is big for electric flocculation, and energy consumption is high, and delivery turbidity is larger；Membrane separation process is being handled
When low concentration wastewater, easily generation concentration polarization leads to film fouling, and energy consumption increases, effluent quality decline.In various processing methods
In, hydroxide precipitation method is most common method, but hydroxide precipitation method can generate a large amount of sludge, need to carry out secondary place
Reason, meanwhile, according to the research of Erdem et al., chromium is easily dissolved out from precipitating sludge in hydroxide precipitating sludge, forms two
Secondary pollution.Thus, it is necessary to research and develop one kind, low energy consumption, Cr without secondary pollution and being able to carry out metal recovery3+Wastewater treatment side
Method.
Electrochemical process is the another kind of water treatment technology to grow up in the past 60 years, has that low energy consumption, without secondary pollution etc.
Feature has very big potentiality in terms of handling heavy metal wastewater thereby.Carbon nanotube is a kind of new carbon of discovery in 1991,
With high-specific surface area, satisfactory electrical conductivity and high mechanical strength, wide application is shown in adsorption treatment water pollution
Prospect.Stainless steel is a kind of common conductive metal material, and resistance to acid and alkali, mechanical strength, electric conductivity are excellent.
Cr3+Mainly with [ Cr (H in solution of the pH less than 42O)6?3+Form exists, and is one with Cr3+Centered on, H2O
For the highly stable regular octahedron structure on vertex.And Cr3+And H2Average bond length between O is 1.99, this makes Cr3+It is difficult to
Electronics is obtained to be reduced.It can be seen that make Cr3+It is easily obtained electronics to be reduced, its stable morphosis need to be changed first,
Increase Cr3+-H2Bond length between O.The good news is when there are the energy such as formic acid, ammonium formate, acetic acid and oxalic acid and Cr in water body3+Hair
When the substance of raw strong complexing, [ Cr (H2O)6?3+Stable positive octahedral structure can be broken, this is conducive to Cr3+Further
It obtains electronics and is reduced to Cr atom, to be removed.
The deposition single-walled carbon nanotube stainless steel mesh sheet that this patent uses electrophoretic deposition to prepare is electrode, with different complexings
Agent assists this Electrode treatment containing Cr3+Waste water improves Cr in waste water whereby3+Removal effect.
Summary of the invention
The purpose of this patent is to remove Cr using different type complexing agent3+, to realize discharged wastewater met the national standard.
Cr will be contained3+Waste water is introduced into reaction chamber, and complexing agent and sodium sulphate is added, the stainless steel modified with single-walled carbon nanotube
For mesh sheet as cathode, titanium net is anode, adjusts reaction chamber pH value, and energization is handled after a certain period of time, simultaneously with spectrophotometer measurement
Calculate Cr3+Removal rate, obtain can qualified discharge waste water.
The complexing agent is one of formic acid, oxalic acid, acetic acid, citric acid.
The complexing agent additive amount is Cr3+Between the 5% ~ 20% of mass fraction.
The pH value controls between 2 ~ 5.
The energization processing, current density are controlled in 0.5 ~ 3mA/cm2Between.
The sodium sulphate, mass fraction are 3 ~ 15g/L.
The energization processing, processing time are 200 ~ 250min.
The reaction chamber is traditional single chamber three-electrode electro Chemical system.In this electro-chemical systems, single-walled carbon nanotube
The stainless steel mesh sheet of modification is cathode, and titanium net is anode, and reference electrode is saturated calomel electrode.Spectrophotometric is used after experiment
Meter measures and calculates Cr3+Removal rate.
The invention has the following beneficial effects:
1, addition different type complexing agent can change Cr3+Form in aqueous solution makes it easier to remove.
2, Cr is being improved3+Energy consumption of reaction is reduced while removal rate.
Detailed description of the invention
Fig. 1 is the different complexing agent Cr of addition3+Removal rate changes over time curve.
Specific embodiment
Embodiment 1
Formic acid assists single-walled carbon nanotube stainless (steel) wire plate electrode to remove Cr3+Waste water:
200mL is contained into Cr3+Waste water (contains Cr3+: 6.13mg/L) it is introduced into reaction chamber, 2g sodium sulphate is added, with single wall carbon
For nanometer tube modified stainless (steel) wire plate electrode as cathode, titanium net is anode, and control reaction chamber pH is 4.0, keeps current density
For 2 mA/cm2, formic acid additive amount is 0.2452mg.The processing time is 210min.Containing Cr3+Waste water after processing, uses spectrophotometric
Meter measures and calculates Cr3+Removal rate shows Cr3+Concentration is reduced to 1.43mg/L, removal rate 76.7%.
What the present embodiment used contains Cr3+Waste water is simulated wastewater.
Embodiment 2
Acetic acid assists single-walled carbon nanotube stainless (steel) wire plate electrode to remove Cr3+Waste water:
200mL is contained into Cr3+Waste water (contains Cr3+: 6.35mg/L) it is introduced into reaction chamber, 1.6g sodium sulphate is added, with single wall carbon
For nanometer tube modified stainless (steel) wire plate electrode as cathode, titanium net is anode, and control reaction chamber pH is 3.5, keeps current density
For 2.2 mA/cm2.Acetic acid additive amount is 0.2540mg.Chemical process time is 240min.Containing Cr3+Waste water after processing, with point
Light photometer measurement simultaneously calculates Cr3+Removal rate shows Cr3+Concentration is reduced to 0.96mg/L, removal rate 84.9%.
What the present embodiment used contains Cr3+Waste water is simulated wastewater.
Embodiment 3
Oxalic acid assists single-walled carbon nanotube stainless (steel) wire plate electrode to remove Cr3+Waste water:
200mL is contained into Cr3+Waste water (contains Cr3+: 6.49mg/L) it is introduced into reaction chamber, 2g sodium sulphate is added, is received with single wall carbon
For the stainless (steel) wire plate electrode of mitron modification as cathode, titanium net is anode, and control reaction chamber pH is 2.5, and holding current density is
2.5 mA/cm2.Oxalic acid additive amount is 0.2596mg.Chemical process time is 240min.Containing Cr3+Waste water after processing, with light splitting
Photometer measurement simultaneously calculates Cr3+Removal rate shows Cr3+Concentration is reduced to 0.51mg/L, removal rate 92.1%.
Embodiment 4
Citric acid assists single-walled carbon nanotube stainless (steel) wire plate electrode to remove Cr3+Waste water:
200mL is contained into Cr3+Waste water (contains Cr3+: 6.30mg/L) it is introduced into reaction chamber, 1.6g sodium sulphate is added, with single wall carbon
For nanometer tube modified stainless (steel) wire plate electrode as cathode, titanium net is anode, and control reaction chamber pH is 3.0, keeps current density
For 2.5 mA/cm2.Citric acid additive amount is 0.2520mg.Chemical process time is 250min.Containing Cr3+Waste water after processing, is used
Spectrophotometer measurement simultaneously calculates Cr3+Removal rate shows Cr3+Concentration is reduced to 0.21mg/L, removal rate 96.7%.
Claims (5)
1. a kind of remove Cr in water removal using different complexing agent assisted electrochemicals3+Method, the specific method is as follows:
Cr will be contained3+Waste water is introduced into reaction chamber, and complexing agent and sodium sulphate is added, and adjusts reaction chamber pH value, and be powered one timing of processing
Between after, with spectrophotometer measurement and calculate Cr3+Removal rate, obtain can qualified discharge waste water；The complexing agent be oxalic acid,
One of citric acid；The energization processing, current density are controlled in 0.5 ~ 3mA/cm2Between；The reaction chamber, with
The stainless steel mesh sheet of single-walled carbon nanotube modification is cathode, and titanium net is anode, and reference electrode is saturated calomel electrode.
2. a kind of different complexing agent assisted electrochemicals of utilization according to claim 1 remove Cr in water removal3+Method, feature
It is that the complexing agent additive amount is Cr3+Between the 5% ~ 20% of mass fraction.
3. a kind of different complexing agent assisted electrochemicals of utilization according to claim 1 remove Cr in water removal3+Method, feature
It is the pH value, controls between 2 ~ 5.
4. a kind of different complexing agent assisted electrochemicals of utilization according to claim 1 remove Cr in water removal3+Method, feature
It is that the sodium sulphate, mass fraction are 3 ~ 15g/L.
5. a kind of different complexing agent assisted electrochemicals of utilization according to claim 1 remove Cr in water removal3+Method, feature
It is the energization processing, the processing time is 200 ~ 250min.
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Citations (1)
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| CN105776444A (en) * | 2016-04-25 | 2016-07-20 | 青岛理工大学 | Method for strengthening Cr(VI) electroreduction by virtue of small molecular inorganic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105776444A (en) * | 2016-04-25 | 2016-07-20 | 青岛理工大学 | Method for strengthening Cr(VI) electroreduction by virtue of small molecular inorganic acid |
Non-Patent Citations (1)
| Title |
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| The electrochemical reduction mechanism of trivalent chromium;Zhixiang Zeng等;《Electrochemistry Communications》;20081209;第11卷(第2期);331-334 |
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