CN103910415A - Three-dimensional graphene nano material electrochemical reactor for treating high-concentration organic wastewater - Google Patents
Three-dimensional graphene nano material electrochemical reactor for treating high-concentration organic wastewater Download PDFInfo
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- CN103910415A CN103910415A CN201410179316.1A CN201410179316A CN103910415A CN 103910415 A CN103910415 A CN 103910415A CN 201410179316 A CN201410179316 A CN 201410179316A CN 103910415 A CN103910415 A CN 103910415A
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Abstract
The invention relates to a three-dimensional graphene nano material electrochemical reactor for treating high-concentration organic wastewater. The reactor comprises a sealed reactor main body, wherein the reactor main body is alternatively and vertically equipped with partition plates for dividing the reactor main body into a plurality of treating units; clamping slots are arranged in the treating units; three-dimensional graphene nano material electrodes are arranged in the clamping slots; titanium electrodes are arranged at the top end inside the reactor main body; a water inlet is arranged on the upper part at one side of the reactor main body; a water outlet is arranged on the lower part at one side, opposite to the water inlet, of the reactor main body; the three-dimensional graphene nano material electrodes arranged in the treating units are in parallel connected with each other and are connected with the titanium electrode by a power supply; and the power supply is a direct-current power supply. According to the invention, the three-dimensional graphene is used as an electrode for applying voltage to improve efficiency of treating organic substances by the three-dimensional graphene, wherein discoloring efficiency can reach 98%-100%, and TOC (total organic carbon) amount removal rate can reach over 96%.
Description
Technical field
The invention belongs to purification of waste water field, relate to a kind of three-dimensional grapheme nano material electrochemical reactor of processing high concentrated organic wastewater.
Background technology
High concentrated organic wastewater generally refers to the waste water of the COD being discharged by industries such as papermaking, leather and food more than 2000mg/L.The composition of this waste water complexity, strong toxicity very, in physical environment, be difficult to photodegradation and biological degradation, biology and environment are caused to very large harm, if directly discharge, can cause serious water environment pollution, therefore the processing of waste water from dyestuff obtained paying attention to widely.General treatment process has: Coagulation Method, oxidation-absorption method, burning method, extraction process, Wet Catalytic Oxidation Method, electrochemical process and membrane separation process, chemical oxidization method, electrolytic process, photodegradation method, biological degradation method etc.Wherein absorption is considered to remove the very effective method of water pollutant, and the energy that it consumes is low, is environmentally friendly method.
Graphene is carbon atom by the hexagonal lattice carbon simple substance forming of neatly arranging, and has the New Two Dimensional crystal carbon nanomaterial of cellular character structure.Based on its chemical structure, Graphene has the physicochemical property of many uniquenesses.For example Graphene has high-specific surface area, high absorption capacity, and surface is also rich in π-electron and can be formed strong π key effect with the organism of aromatic structure, so obtained paying close attention to widely in water treatment field.But because two-dimentional grapheme material is suspension in the aqueous solution, be difficult to separate, easily cause secondary pollution, as the method for the filtration with traditional separates, can cause the obstruction of filter and the loss of grapheme material.
Chinese patent literature CN101812702A (application number: 201010168663.6) disclose a kind of three-phase three-dimensional electrochemical reactor.This three-phase three-dimensional electrochemical reactor, comprise electrolyzer, described electrolyzer is provided with anode electrode, two cathode electrodes and working electrode, described working electrode is the gac of conduction and the mixture of the gac of process insulation processing, and the gac of electroconductibility is 1: 4～4: 1 with the quality of activated carbon ratio through insulation processing; Described working electrode loading microorganisms, forms microbial film.But the disclosed electrochemical reactor electrode of above-mentioned patent documentation is gac material, electrochemical treatment poor effect, and also the contact area of electrode and waste water is little, can not react with wastewater electrochemical fully.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of three-dimensional grapheme nano material electrochemical reactor of processing high concentrated organic wastewater.
Technical scheme of the present invention is as follows:
A kind of three-dimensional grapheme nano material electrochemical reactor of processing high concentrated organic wastewater, this reactor comprises airtight reactor body, the staggered dividing plate that is vertically provided with of described reactor body, reactor body is divided into multiple processing units by described dividing plate, in described processing unit, be provided with clip slot, in described clip slot, be provided with three-dimensional grapheme nano material electrode, the inner tip of described reactor body is provided with titanium electrode, one upper lateral part of described reactor body is provided with water-in, the bottom of the side that described reactor body is relative with water-in is provided with water outlet, the described three-dimensional grapheme nano material electrode being arranged in processing unit is connected in parallel to each other and is connected with titanium electrode by power supply, described power supply is direct supply,
Described three-dimensional grapheme nano material electrode prepares as follows: after the ultrasonic 10～30min of graphene oxide solution that is 1～1.5mg/ml by concentration, add 0.5%～2% xitix of graphene oxide solution quality, ultrasonic 5～10min forms uniform solution again, under the condition of 85～95 DEG C, heats 1～1.5h; Clean, cooling, dry, to obtain final product.
According to the present invention, preferred, described reactor body long 35～50cm, high 30～40cm, wide 15～30cm.
According to the present invention, preferred, the number of described dividing plate is 2～5.
According to the present invention, preferred, the height of described clip slot is 20～30cm, and the spacing of clip slot and reactor body bottom is 5cm.
According to the present invention, preferred, described voltage of supply is 0.5～1.5V.
According to the present invention, preferably, in the preparation method of described three-dimensional grapheme nano material electrode, the concentration of graphene oxide solution is 1.2～1.5mg/ml, the add-on of xitix is 1%～1.5% of graphene oxide solution quality, cleaning way is the mode of dialysis, and cooling temperature is-10～-20 DEG C, and drying mode is dry 24～48h in the vacuum freeze drier device of-40～-50 DEG C.
The shape of three-dimensional grapheme nano material of the present invention can according to not from need to be made into different shapes, preferably rectangular-shaped.When preparation, the graphene oxide solution that adds xitix is put into after the container reaction of desired shape, cleaned, cooling, be dried, can obtain the three-dimensional grapheme nano material electrode of desired shape.
The present invention reacts graphene oxide and xitix, by pi-pi accumulation effect in Graphene carbon atomic layer, and hydrophobic interaction, make three-dimensional grapheme material, when three-dimensional grapheme adsorb organic compound, utilize electrochemical principle to process organism.
Beneficial effect of the present invention:
1, three-dimensional grapheme nano material electrode of the present invention not only has high-specific surface area, and is easy to separate with water and can cause secondary pollution, can substitute Graphene and carry out the processing for organic waste water.
2, in Graphene, the movement rate of electronics has reached 1/300 of the light velocity, far exceed the movement velocity of electronics in general conductor, utilize the present invention of this characteristic to improve three-dimensional grapheme and process organic efficiency by applying voltage three-dimensional grapheme as electrode, percent of decolourization can reach 98%～100%, TOC amount clearance can reach more than 96%.
3, the present invention is using graphene oxide as starting material, with low cost, passes into low voltage (only 0.5～1.5V) and can play good removal effect, and energy consumption is low.
4, three-dimensional grapheme material electrode toughness of the present invention is strong, difficult broken, and performance stability is good, and processing efficiency is high, stable effluent quality, flow process is simple, facility compact, floor space is little, economically feasible, non-secondary pollution easily, realize automatically and controlling, operational management is simple.
Brief description of the drawings
Fig. 1 is the agent structure schematic diagram of the embodiment of the present invention 1 three-dimensional grapheme nano material electrochemical reactor.
Fig. 2 is the side-view of the embodiment of the present invention 1 three-dimensional grapheme nano material electrochemical reactor.
Fig. 3 is the vertical view of the embodiment of the present invention 1 three-dimensional grapheme nano material electrochemical reactor.
Wherein, 1, reactor body, 2, dividing plate, 3, clip slot, 4, three-dimensional grapheme nano material electrode, 5, titanium electrode, 6, water-in, 7, water outlet, 8, power supply, 9, pump.
Embodiment
Below by specific embodiment, the present invention will be further described, but be not limited to this.
Embodiment 1
A kind of three-dimensional grapheme nano material electrochemical reactor of processing high concentrated organic wastewater, this reactor comprises airtight reactor body 1, the staggered dividing plate 2 that is vertically provided with of described reactor body 1, reactor body 1 is divided into multiple processing units by described dividing plate 2, in described processing unit, be provided with clip slot 3, in described clip slot 3, be provided with three-dimensional grapheme nano material electrode 4, the inner tip of described reactor body 1 is provided with titanium electrode 5, one upper lateral part of described reactor body 1 is provided with water-in 6, the bottom of the side that described reactor body 1 is relative with water-in 6 is provided with water outlet 7, the described three-dimensional grapheme nano material electrode 4 being arranged in processing unit is connected in parallel to each other and is connected with titanium electrode 5 by power supply 8, described power supply 8 is direct supply,
Described three-dimensional grapheme nano material electrode 4 prepares as follows: after the ultrasonic 30min of graphene oxide solution that is 1.5mg/ml by concentration, add 2% xitix of graphene oxide solution quality, ultrasonic 10min forms uniform solution again, under the condition of 90 DEG C, heats 1h; Mode by dialysis is cleaned, and is cooled to-20 DEG C, and in the vacuum freeze drier device of-50 DEG C, dry 24h, to obtain final product.
The long 36cm of reactor body 1, high 30cm, wide 15cm in the present embodiment, the number of dividing plate 2 is 2, and the height of clip slot 3 is 20cm, and clip slot 3 is 5cm with the spacing of reactor body 1 bottom; Three-dimensional grapheme nano material electrode 4 be shaped as rectangular parallelepiped, titanium electrode 5 is titanium mesh, voltage of supply is 1.2V.
When the three-dimensional grapheme nano material electrochemical reactor of the present embodiment uses, the water outlet 7 of off-response device, high concentrated organic wastewater is pumped into reactor from water-in 6 with pump 9, open power supply 8, three-dimensional grapheme nano material electrode 4 carries out electrochemical treatment to high concentrated organic wastewater, after finishing dealing with, open water outlet 7, complete the electrochemical treatment to high concentrated organic wastewater.
Experimental example 1
Utilize the three-dimensional grapheme nano material electrochemical reactor of embodiment 1 to Xylene Red 27 (Acid Red27) high concentrated organic wastewater electrochemical treatment, the original index of Acid Red27 high concentrated organic wastewater is Acid red27:2000mg/L, total content of organic carbon (TOC) 720mg/L.
Step is as follows:
The water outlet 7 of off-response device, Acid Red27 high concentrated organic wastewater is pumped into reactor from water-in 6 with pump 9, open power supply 8 (voltage of supply 1.2V), three-dimensional grapheme nano material electrode 4 carries out electrochemical treatment 1h to Acid Red27 high concentrated organic wastewater, after finishing dealing with, open water outlet 7, collect water outlet and survey percent of decolourization, TOC amount at water outlet 7, and relatively calculate its percent of decolourization and TOC clearance with the original index of Acid Red27 high concentrated organic wastewater.
As calculated, under the condition of constant voltage that applies 1.2V, process 1h, Acid Red27 high concentrated organic wastewater percent of decolourization is that 100%, TOC amount clearance is 99%.
Embodiment 2
Three-dimensional grapheme nano material electrochemical reactor as described in Example 1, that different is the long 40cm of reactor body 1, high 35cm, wide 20cm, and the number of dividing plate 2 is 3, and the height of clip slot 3 is 25cm, and clip slot 3 is 5cm with the spacing of reactor body 1 bottom; Three-dimensional grapheme nano material electrode 4 be shaped as rectangular parallelepiped, titanium electrode 5 is titanium mesh, voltage of supply is 0.6V.
Embodiment 3
Three-dimensional grapheme nano material electrochemical reactor as described in Example 1, that different is the long 50cm of reactor body 1, high 40cm, wide 30cm, and the number of dividing plate 2 is 5, and the height of clip slot 3 is 30cm, and clip slot 3 is 5cm with the spacing of reactor body 1 bottom; Three-dimensional grapheme nano material electrode 4 be shaped as rectangular parallelepiped, titanium electrode 5 is titanium mesh, voltage of supply is 1.0V.
Claims (8)
1. process the three-dimensional grapheme nano material electrochemical reactor of high concentrated organic wastewater for one kind, it is characterized in that: this reactor comprises airtight reactor body, the staggered dividing plate that is vertically provided with of described reactor body, reactor body is divided into multiple processing units by described dividing plate, in described processing unit, be provided with clip slot, in described clip slot, be provided with three-dimensional grapheme nano material electrode, the inner tip of described reactor body is provided with titanium electrode, one upper lateral part of described reactor body is provided with water-in, the bottom of the side that described reactor body is relative with water-in is provided with water outlet, the described three-dimensional grapheme nano material electrode being arranged in processing unit is connected in parallel to each other and is connected with titanium electrode by power supply, described power supply is direct supply,
Described three-dimensional grapheme nano material electrode prepares as follows: after the ultrasonic 10～30min of graphene oxide solution that is 1～1.5mg/ml by concentration, add 0.5%～2% xitix of graphene oxide solution quality, ultrasonic 5～10min forms uniform solution again, under the condition of 85～95 DEG C, heats 1～1.5h; Clean, cooling, dry, to obtain final product.
2. the three-dimensional grapheme nano material electrochemical reactor of processing high concentrated organic wastewater according to claim 1, is characterized in that: described reactor body long 35～50cm, high 30～40cm, wide 15～30cm.
3. the three-dimensional grapheme nano material electrochemical reactor of processing high concentrated organic wastewater according to claim 1, is characterized in that: the number of described dividing plate is 2～5.
4. the three-dimensional grapheme nano material electrochemical reactor of processing high concentrated organic wastewater according to claim 1, is characterized in that: the height of described clip slot is 20～30cm, and the spacing of clip slot and reactor body bottom is 5cm.
5. the three-dimensional grapheme nano material electrochemical reactor of processing high concentrated organic wastewater according to claim 1, is characterized in that: described voltage of supply is 0.5～1.5V.
6. the three-dimensional grapheme nano material electrochemical reactor of processing high concentrated organic wastewater according to claim 1, it is characterized in that: in the preparation method of described three-dimensional grapheme nano material electrode, the concentration of graphene oxide solution is 1.2～1.5mg/ml.
7. the three-dimensional grapheme nano material electrochemical reactor of processing high concentrated organic wastewater according to claim 1, is characterized in that: the add-on of xitix is 1%～1.5% of graphene oxide solution quality.
8. the three-dimensional grapheme nano material electrochemical reactor of processing high concentrated organic wastewater according to claim 1, it is characterized in that: cleaning way is the mode of dialysis, cooling temperature is-10～-20 DEG C, and drying mode is dry 24～48h in the vacuum freeze drier device of-40～-50 DEG C.
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| CN201410179316.1A CN103910415B (en) | 2014-04-29 | 2014-04-29 | Three-dimensional graphene nano material electrochemical reactor for treating high-concentration organic wastewater |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152421A (en) * | 2015-09-11 | 2015-12-16 | 东莞市绿巨人环境科技有限公司 | Treatment method of distillation extraction waste liquid in fine chemical engineering production |
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| US4161435A (en) * | 1977-10-13 | 1979-07-17 | Innova, Inc. | Process and apparatus for reducing the level of contaminants in aqueous electrolytes containing the same |
| CA2758096A1 (en) * | 2009-04-06 | 2010-10-14 | Sa Envitech S.R.L. | Graphene based electrodes for electrochemical reactions, and electrooxidation process for the removal of contaminants from liquids using said electrodes |
| CN102225331A (en) * | 2011-04-03 | 2011-10-26 | 长安大学 | Particle electrode catalyst filling material for three-dimensional electrodes and preparation method thereof |
| WO2012013221A1 (en) * | 2010-07-27 | 2012-02-02 | Siemens Aktiengesellschaft | Apparatus for water treatment and method of manufacture thereof |
| CN103058335A (en) * | 2013-01-17 | 2013-04-24 | 山东大学 | Novel graphene-Ti electrode printing and dyeing wastewater treatment electrochemical reactor |
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2014
- 2014-04-29 CN CN201410179316.1A patent/CN103910415B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4161435A (en) * | 1977-10-13 | 1979-07-17 | Innova, Inc. | Process and apparatus for reducing the level of contaminants in aqueous electrolytes containing the same |
| CA2758096A1 (en) * | 2009-04-06 | 2010-10-14 | Sa Envitech S.R.L. | Graphene based electrodes for electrochemical reactions, and electrooxidation process for the removal of contaminants from liquids using said electrodes |
| WO2012013221A1 (en) * | 2010-07-27 | 2012-02-02 | Siemens Aktiengesellschaft | Apparatus for water treatment and method of manufacture thereof |
| CN102225331A (en) * | 2011-04-03 | 2011-10-26 | 长安大学 | Particle electrode catalyst filling material for three-dimensional electrodes and preparation method thereof |
| CN103058335A (en) * | 2013-01-17 | 2013-04-24 | 山东大学 | Novel graphene-Ti electrode printing and dyeing wastewater treatment electrochemical reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105152421A (en) * | 2015-09-11 | 2015-12-16 | 东莞市绿巨人环境科技有限公司 | Treatment method of distillation extraction waste liquid in fine chemical engineering production |
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Effective date of registration: 20180621 Address after: 250000 Building 1, No. 88 Convention and Exhibition Road, Hi-tech Zone, Ji'nan, Shandong 1-1503 Patentee after: Ji'nan Voda Environmental Protection Technology Co., Ltd. Address before: No. 27, mountain Dana Road, Ji'nan City, Shandong, Shandong Patentee before: Shandong University |
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