CN105478101A - Reduced graphene oxide/titanium dioxide composite wastewater treatment agent, and preparation method and application thereof - Google Patents
Reduced graphene oxide/titanium dioxide composite wastewater treatment agent, and preparation method and application thereof Download PDFInfo
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- CN105478101A CN105478101A CN201510824543.XA CN201510824543A CN105478101A CN 105478101 A CN105478101 A CN 105478101A CN 201510824543 A CN201510824543 A CN 201510824543A CN 105478101 A CN105478101 A CN 105478101A
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- titanium dioxide
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention belongs to the field of functional materials, and discloses a reduced graphene oxide/titanium dioxide composite wastewater treatment agent, and a preparation method and an application thereof. The preparation method comprises the following steps: adding graphene oxide and titanium dioxide titanium dioxide to a water/ethanol mixture, and carrying out ultrasonic treatment and stirring dispersion to obtain a reaction suspension; and placing the reaction suspension in a reaction kettle, reacting at 140-160DEG C under 0.55-0.65MPa for 1-2h, cooling the obtained reaction product, filtering the cooled reaction product, washing the filtered reaction product, and drying the washed reaction product to obtain the reduced graphene oxide/titanium dioxide composite wastewater treatment agent. The wastewater treatment agent can effectively reduce COD in tobacco slice wastewater and has a good photocatalysis effect; and the preparation method has the advantages of simplicity and easy operation.
Description
Technical field
The invention belongs to field of functional materials, be specifically related to a kind of redox graphene/titanium dioxide compound wastewater inorganic agent and preparation method thereof and the application in tobacco sheet production wastewater process.
Background technology
Graphene is a kind of novel Two-dimensional Carbon material, and its basic structure is sp
2the honeycomb type carbocyclic ring structure of hydridization, has specific area large, the advantages such as conduction, heat conduction and physical property are good.Graphene oxide, is a kind of important derivatives of Graphene, its carbon skeleton exists a large amount of oxygen-containing functional groups, as fat (virtue) ether, hydroxyl, carboxyl, carbonyl etc.Just because of such design feature, make graphene oxide not only have the feature of Graphene bigger serface, also have a distinct increment in reactivity worth simultaneously, can field of waste water treatment be applied to by other current material of compound.
Tobacco business remains high because of the demand in market to the pollution of environment, although in recent years, make moderate progress because of the introducing of tobacco sheets by paper making method technology, the process of tobacco sheet production wastewater proposes a new difficult problem to environmental protection again.Be different from the factory effluent of traditional tobacco business, the features such as it is large that tobacco sheet production wastewater has composition fluctuation, difficult.
Therefore, develop a kind of tobacco sheet production wastewater inorganic agent of graphite oxide thiazolinyl, not only enriched the kind of graphite oxide olefinic base material, and the unmanageable problem of tobacco sheet production wastewater can be solved, be of practical significance very much.
Summary of the invention
For solving the shortcoming and defect part of prior art, primary and foremost purpose of the present invention is the preparation method providing a kind of redox graphene/titanium dioxide compound wastewater inorganic agent.
Another object of the present invention is to the redox graphene/titanium dioxide compound wastewater inorganic agent providing above-mentioned preparation method to obtain.
Another object of the present invention is the application providing above-mentioned redox graphene/titanium dioxide compound wastewater inorganic agent.
The object of the invention is achieved through the following technical solutions:
A preparation method for redox graphene/titanium dioxide compound wastewater inorganic agent, comprises the following steps:
Graphene oxide and titanium dioxide are added in water/alcohol mixture, ultrasonic agitation is disperseed, and obtains reaction suspension; Then reaction suspension is placed in reactor, in 140 ~ 160 DEG C, pressure is react 1 ~ 2h under the condition of 0.55 ~ 0.65MPa, cooling, filters, washing, dry, obtains redox graphene/titanium dioxide compound wastewater inorganic agent.
The mass ratio of described graphene oxide and titanium dioxide is 1:5 ~ 1:15; In described water/alcohol mixture, the volume ratio of water and ethanol is 1:1 ~ 3:1.
In described reaction suspension, the mass fraction of graphene oxide is 1 ~ 3 ‰.
Described ultrasonic power is 800 ~ 1000W, and described speed of agitator is 300 ~ 400r/min, and described jitter time is 10 ~ 20min.
The temperature of described cooling is room temperature, and described washing refers to and adopts deionized water washing.
Described washing times is 3 ~ 5 times; Described baking temperature is 45 ~ 55 DEG C, and the dry time is 12 ~ 36h.
Described redox graphene/titanium dioxide compound wastewater inorganic agent is prepared by above-mentioned preparation method.
The waste water that described redox graphene/titanium dioxide compound wastewater inorganic agent is produced for the treatment of reconstituted tobacoo, described waste water treating agent effectively can reduce the COD of tobacco sheet production wastewater.
Compared with prior art, the present invention has the following advantages and beneficial effect:
The redox graphene that the present invention obtains/titanium dioxide compound wastewater inorganic agent effectively can reduce the COD (initial value > 500mg/L) of tobacco sheet production wastewater to below 65mg/L, photocatalysis effect is good, and preparation technology is simple, be easy to operation.
Detailed description of the invention
Below in conjunction with enforcement, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.In the present invention, each initiation material can be buied from market or conventionally method prepares.
Embodiment 1
A preparation method for redox graphene/composite titania material, comprises the following steps:
Be that successively to join volume ratio be in the water/alcohol mixture of 1:1 for the graphene oxide of 1:5 and titanium dioxide by mass ratio, and with the rotating speed dispersed with stirring 20min of 300r/min under the ultrasonic vibration condition of power 800W, obtain the reaction suspension that mass fraction is 1 ‰; Then reaction suspension being put into temperature is 140 DEG C, pressure is the reaction kettle for reaction 2h of 0.55MPa, reaction treats that solution is cooled to room temperature after stopping, filter and spend deionized water filter cake 3 times, 45 DEG C of dry 36h, obtain redox graphene/composite titania material (i.e. waste water treating agent).The surface area parameters of described redox graphene/composite titania material and titanium dioxide is as shown in table 1.
The surface area characterization result of table 1 titanium dioxide and composite
| Titanium dioxide | Composite | |
| BET surface area (m 2/g) | 40.46 | 55.66 |
| Langmuir surface area (m 2/g) | 54.3 | 75.02 |
Table 1 lists the BET surface area characterization result of titanium dioxide and redox graphene/composite titania material.Can obviously find out, because the existence of graphene oxide, the BET surface area of composite comparatively titanium dioxide significantly improves.In photocatalytic process, the BET surface area of catalyst is larger, more can promote that it is to the absorption of treated object, be conducive to reaching higher photocatalysis efficiency.
Embodiment 2
A preparation method for redox graphene/composite titania material, comprises the following steps:
Be that successively to join volume ratio be in the water/alcohol mixture of 1:1 for the graphene oxide of 1:5 and titanium dioxide by mass ratio, and stir 15min with the rotating speed of 350r/min under the ultrasonic vibration condition of power 900W, obtain the reaction suspension that mass fraction is 1 ‰; Then reaction suspension being put into temperature is 150 DEG C, pressure is the reaction kettle for reaction 1.5h of 0.6MPa, and reaction treats that solution is cooled to room temperature after stopping, and filters and spends deionized water filter cake 4 times, 50 DEG C of dry 24h, obtain redox graphene/composite titania material and waste water treating agent.
Embodiment 3
A preparation method for redox graphene/composite titania material, comprises the following steps:
Be that successively to join volume ratio be in the water/alcohol mixture of 1:1 for the graphene oxide of 1:5 and titanium dioxide by mass ratio, and 10min is stirred with the rotating speed of 400r/min under the ultrasonic vibration condition of power 1000W, obtain the reaction suspension that mass fraction is 1 ‰; Then reaction suspension being put into temperature is 160 DEG C, pressure is the reaction kettle for reaction 1h of 0.65MPa, and reaction treats that solution is cooled to room temperature after stopping, and filters and spends deionized water filter cake 5 times, 55 DEG C of dry 12h, obtain redox graphene/composite titania material and waste water treating agent.
Embodiment 4 application testing
Redox graphene/composite titania material reduces the test of tobacco sheet production wastewater:
Redox graphene/the composite titania material prepare embodiment 1 ~ 3 and zeolite (Jinyun county, Zhejiang province clinoptilolite) and titanium dioxide (Aladdin reagent (Shanghai) Co., Ltd.) reduce the performance that reconstituted tobacoo produces COD and detect respectively:
Get zeolite, titanium dioxide, the redox graphene/composite titania material of embodiment 1 ~ 3 and waste water treating agent 1g, to join in the tobacco sheet production wastewater of 400mL initial COD value > 500mg/L ultrasonic 10min under normal temperature respectively, then 1h is processed under the ultraviolet light being 8W at power, again with the centrifugal 10min of the rotating speed of 10000r/min, finally utilize the COD value in the rapid-digestion spectrophotometry centrifuged supernatant in GB HJ/T399-2007.Test result is as shown in table 2.
The composite that table 2 embodiment 1 ~ 3 is obtained and conventional material reduce the result of tobacco sheet production wastewater COD
As can be seen from Table 2, it is many that this redox graphene/composite titania material reduces that the effect of tobacco sheet production wastewater COD will be good than zeolite and ordinary titanium dioxide.
The present invention adopts the Hummers legal system of improvement for graphene oxide:
First carry out the pre-oxidation of graphite: in the round-bottomed flask of 250mL, add the 120mL concentrated sulfuric acid, more successively add the K of 12.5g
2s
2o
8with the P of 12.5g
2o
5, add 5g graphite powder after stirring, fully after mixing, round-bottomed flask is put into thermostat water bath, equilibrium temperature is 80 DEG C, reacts 6 hours; After reaction terminates, slowly add distilled water diluting suspension and no longer change to temperature, wash further, suction filtration is to filtrate pH in neutral, and dry cake, namely obtains pre-oxidation graphite.
Then be oxidized: in the round-bottomed flask of 500mL, add the 69mL concentrated sulfuric acid, then add 1.5gNaNO
3, after it dissolves completely, add 3g pre-oxidation graphite again and stir, course of reaction comprises three phases: in (1) low-temp reaction stage, round-bottomed flask is put into ice-water bath, under the condition of strong stirring, slowly add 9gKMnO
4, the stage of reaction ensures that temperature is no more than 20 DEG C, insulation 30min, and suspension becomes blackish green from black purple gradually; (2) the warm stage of reaction in, be warming up to 35 ± 3 DEG C after removing ice bath and continue reaction, and in 15min, slowly add 140mL water under agitation, suspension gradually becomes aubergine; (3) the pyroreaction stage, be warming up to 60 DEG C and add the H of 100mL6%
2o
2solution, suspension gradually becomes glassy yellow; Add the dense HCl of 10mL to remove unreacted hydrogen peroxide after reaction terminates, then repeatedly with the hot wash filter cake of 60 DEG C to pH in neutrality; Again be dispersed in water by filter cake, ultrasonic process 1h, the brown solution obtained, subsequently with the centrifugal 10min of 10000rpm, removes black solid precipitation; Finally, supernatant is dialysed one week to remove salt impurity, be drying to obtain graphene oxide solid.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. a preparation method for redox graphene/titanium dioxide compound wastewater inorganic agent, is characterized in that, comprise the following steps:
Graphene oxide and titanium dioxide are added in water/alcohol mixture, ultrasonic agitation is disperseed, and obtains reaction suspension; Then reaction suspension is placed in reactor, in 140 ~ 160 DEG C, pressure is react 1 ~ 2h under the condition of 0.55 ~ 0.65MPa, cooling, filters, washing, dry, obtains redox graphene/titanium dioxide compound wastewater inorganic agent.
2. the preparation method of redox graphene/titanium dioxide compound wastewater inorganic agent according to claim 1, is characterized in that: the mass ratio of described graphene oxide and titanium dioxide is 1:5 ~ 1:15; In described water/alcohol mixture, the volume ratio of water and ethanol is 1:1 ~ 3:1; In described reaction suspension, the mass fraction of graphene oxide is 1 ~ 3 ‰.
3. the preparation method of redox graphene/titanium dioxide compound wastewater inorganic agent according to claim 1, it is characterized in that: described ultrasonic power is 800 ~ 1000W, described speed of agitator is 300 ~ 400r/min, and described jitter time is 10 ~ 20min.
4. the preparation method of redox graphene/titanium dioxide compound wastewater inorganic agent according to claim 1, is characterized in that: the temperature of described cooling is room temperature, and described washing refers to and adopts deionized water washing.
5. the preparation method of redox graphene/titanium dioxide compound wastewater inorganic agent according to claim 1, is characterized in that: described washing times is 3 ~ 5 times; Described baking temperature is 45 ~ 55 DEG C, and the dry time is 12 ~ 36h.
6. the redox graphene prepared by preparation method described in any one of Claims 1 to 5/titanium dioxide compound wastewater inorganic agent.
7. the application of redox graphene/titanium dioxide compound wastewater inorganic agent according to claim 6, is characterized in that: the waste water that described redox graphene/titanium dioxide compound wastewater inorganic agent is produced for the treatment of reconstituted tobacoo.
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| CN201510824543.XA CN105478101A (en) | 2015-11-24 | 2015-11-24 | Reduced graphene oxide/titanium dioxide composite wastewater treatment agent, and preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107416941A (en) * | 2017-07-21 | 2017-12-01 | 张娟 | A kind of titanium dioxide waste water treating agent and preparation method thereof |
| CN107469636A (en) * | 2017-09-14 | 2017-12-15 | 辽宁兰晶科技有限公司 | A kind of rGO/TiO2The preparation method and application of photocatalysis filter membrane |
| CN110002642A (en) * | 2019-04-10 | 2019-07-12 | 华东交通大学 | A kind of photochemical catalytic oxidation technique for coking wastewater |
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| CN102513079A (en) * | 2011-11-22 | 2012-06-27 | 南京工业大学 | Controllable crystalline form titanium dioxide and graphite alkene composite material with high efficient photoelectricity activity and preparation method thereof |
| WO2013062306A2 (en) * | 2011-10-24 | 2013-05-02 | 포항공과대학교 산학협력단 | High purity graphene synthesis melted in water through photocatalytic reaction |
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| WO2013062306A2 (en) * | 2011-10-24 | 2013-05-02 | 포항공과대학교 산학협력단 | High purity graphene synthesis melted in water through photocatalytic reaction |
| CN102489285A (en) * | 2011-11-22 | 2012-06-13 | 浙江大学 | Preparation method of graphene-titanium dioxide composite photocatalyst |
| CN102513079A (en) * | 2011-11-22 | 2012-06-27 | 南京工业大学 | Controllable crystalline form titanium dioxide and graphite alkene composite material with high efficient photoelectricity activity and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107416941A (en) * | 2017-07-21 | 2017-12-01 | 张娟 | A kind of titanium dioxide waste water treating agent and preparation method thereof |
| CN107469636A (en) * | 2017-09-14 | 2017-12-15 | 辽宁兰晶科技有限公司 | A kind of rGO/TiO2The preparation method and application of photocatalysis filter membrane |
| CN110002642A (en) * | 2019-04-10 | 2019-07-12 | 华东交通大学 | A kind of photochemical catalytic oxidation technique for coking wastewater |
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Application publication date: 20160413 |