CN107352661A - A kind of graphene oxide fatty amine scavenger and its application process - Google Patents

A kind of graphene oxide fatty amine scavenger and its application process Download PDF

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Publication number
CN107352661A
CN107352661A CN201710519510.3A CN201710519510A CN107352661A CN 107352661 A CN107352661 A CN 107352661A CN 201710519510 A CN201710519510 A CN 201710519510A CN 107352661 A CN107352661 A CN 107352661A
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graphene oxide
fatty amine
graphite
scavenger
suspension
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CN107352661B (en
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李洪强
丁刚
丁一刚
何东升
翁孝卿
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Wuhan Institute of Technology
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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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/301—Detergents, surfactants
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen

Abstract

The invention discloses a kind of graphene oxide fatty amine scavenger and its application process, prepares graphite oxide using native graphite, first pickling is washed, is then centrifuged for again；By the graphite oxide vacuum freeze drying 24 72 hours after centrifugation, dried graphite oxide is clayed into power, and be dispersed in water；Ultrasound is carried out to graphite oxide solution and peels off 5 15min；Suspension after stripping is centrifuged, it is graphene oxide fatty amine scavenger to take supernatant liquor.The scavenger of preparation and the waste water of fatty amine mix, vibration, adsorbing and removing reaction；Finally, scavenger is reclaimed using Bubble-floating Method, obtains scavenger and purified water after adsorption reaction.The present invention prepares graphene oxide suspension using cheap and rich reserves graphite as raw material, using the Hummer methods of maturation, low-cost industrial can prepare well；It can be directly used for removing fatty amine, absorption property is good and separation of solid and liquid is simple, has good prospects for commercial application.

Description

A kind of graphene oxide fatty amine scavenger and its application process
Technical field
It is the present invention relates to a kind of graphene oxide fatty amine scavenger and preparation method thereof and useless using scavenger removing Fatty amine method in water.
Background technology
The usage amount of surfactant increases year by year, and use range constantly expands, the harm to health and environment It is increasingly severe.Harm of the surfactant to health, which is mainly reflected in it, has chronic toxicity, can cause hemoglobin, The change of red blood cell and quantity of leucocyte, and the skin of people is damaged.The concentration of surfactant reaches 1mgL-1 When, surfactant can form a large amount of foams in water body, not only have impact on the landscape of natural water, and the water surface formed every Absciss layer, so as to reduce the dissolving of oxygen and transfer rate, the gas exchanges between water and air are reduced, cause water quality deterioration.With Water irrigated farmland containing surfactant, can be such that the leaf of crops slowly crimps, and root gradually becomes thin and short, and palm fibre occurs in epiblem The aging phenomenon of color fleck, the yield of crops are severely impacted.Fail the surfactant being degraded in a large amount of water bodys After adsorption by soil, suction-operated of the soil to organic poison is significantly reduced, and Soil Microorganism may be changed Composition, indirect pollution is caused to environment, therefore pollution of the surfactant to water body is increasingly by government department and people Concern.
China's oxidation ore resources (including non-ferrous metal oxide ore) have the characteristics of " poor, thin, miscellaneous ", and flotation turns at present most Conventional dressing method, and fatty amine (surfactant) is wide variety of a kind of flotation collecting in oxide ore flotation operation Agent.In oxide ore flotation process, in order to improve the utilization rate of fresh water, the tailing water after sorting needs to recycle, and causes collecting Agent fatty amine is constantly enriched with ore dressing plant flotation water circulation system.Fatty amine ion enters flotation system with recirculated water, causes Flotation froth is excessively stable, makes final sorting index undesirable.Contain elemental nitrogen in fatty amine collecting agent, fatty amine gives up Body eutrophication will be caused by being arranged outside water, be disturbed ecological stability.Thus, the fatty amine collecting agent in beneficiation wastewater is removed, will be had The protection of cycle applications or mining area ecological environment beneficial to waste water.
Surfactant removal methods are a lot, there is catalytic oxidation, biological degradation method, supercritical ultrasonics technology, micro-electrolysis method, biology Edman degradation Edman etc., most methods have its drawback, and such as processing cost is high, effect is poor, can bring secondary pollution.Absorption method is profit Porous and big specific surface area with adsorbent, the pollutant in waste water is adsorbed on surface so as to reach separation purpose.
Physisorphtion advantage is that speed is fast, stability is good, equipment occupation of land is small.Therefore need a kind of adsorption capacity height badly, inhale The adsorbent that attached effect is good, easy scale is combined to, cost is relatively low, easily reclaims.
The content of the invention
Based on above the deficiencies in the prior art, technical problem solved by the invention is to provide a kind of processing cost low Honest and clean, high treating effect, and remove after pollutant easily the graphene oxide fatty amine scavenger of high efficiente callback and its preparation side Method, and graphene oxide can be reclaimed by Bubble-floating Method after use, fatty amine can be eliminated ecological environment or flotation zone are come Negative effect.
In order to solve the above-mentioned technical problem, the present invention provides a kind of graphene oxide fatty amine scavenger, it is characterised in that： Graphene oxide suspension comprising 0.1~5g/L.
As the preferred of above-mentioned technical proposal, under graphene oxide fatty amine scavenger provided by the invention further comprises Row technical characteristic it is part or all of：
As the improvement of above-mentioned technical proposal, described graphene oxide suspension is to prepare gained using Hummer methods Graphene oxide suspension.
As the improvement of above-mentioned technical proposal, described Hummer methods prepare graphene oxide suspension, include following step Suddenly：
Step 1: preparing graphite oxide using native graphite, the graphite oxide prepared first is carried out to pickling and washed again, most Centrifuge again afterwards；
Step 2: by the graphite oxide vacuum freeze drying 24-72 hours after centrifugation, dried graphite oxide is worn into Powder；
Step 3: graphite oxide powder is dispersed in water；
Step 4: carrying out ultrasound to graphite oxide solution peels off 5-15min；
Step 5: the suspension after stripping is centrifuged, it is graphene oxide fatty amine scavenger to take supernatant liquor.
As the preferred of above-mentioned technical proposal, the preparation method of graphene oxide fatty amine scavenger provided by the invention is entered One step includes the part or all of of following technical characteristic：
As the improvement of above-mentioned technical proposal, in the step 1, native graphite is crystalline flake graphite, block graphite or cryptocrystalline One kind in graphite.
As the improvement of above-mentioned technical proposal, in the step 3, graphite oxide is with water according to 0.6-1.2g：1L ratio Example mixing.
As the improvement of above-mentioned technical proposal, graphene oxide is dense in the obtained graphene oxide fatty amine scavenger Spend for 0.1~5g/L.
A kind of application process using graphene oxide fatty amine scavenger, it is characterised in that comprise the following steps：
S1 prepares graphene oxide suspension using native graphite as raw material, using Hummer methods；
S2 takes the waste water of fatty amine, the object as processing；
S3 graphene oxide suspensions mix with waste water；
S4 vibrates the mixed liquor obtained by S3, adsorbing and removing；
S5 stirs the graphene oxide suspension after adsorption reaction, flotation, and graphene oxide hydrophobization floc sedimentation is carried out Air supporting is reclaimed, and is obtained the graphene oxide after adsorption reaction and is stripped of the purified water of fatty amine.
As the preferred of above-mentioned technical proposal, the application side provided by the invention using graphene oxide fatty amine scavenger Method further comprises the part or all of of following technical characteristic：
As the improvement of above-mentioned technical proposal, the native graphite described in step S1 is crystalline flake graphite, block graphite or cryptocrystalline One kind in graphite.
As the improvement of above-mentioned technical proposal, primary amine that the fatty amine described in S2 is carbon chain lengths in the range of C8- C22, One kind in secondary amine and tertiary amine and polyamines, the concentration of the fatty amine is 10~5000mg/L.
As the improvement of above-mentioned technical proposal, the volume ratio 1% of graphene oxide suspension and waste water described in S3~ 50%.
As the improvement of above-mentioned technical proposal, the adsorption reaction condition described in S4 is 5 DEG C~40 DEG C of adsorption temp, vibration Device rotating speed 50r/min~300r/min, adsorbing and removing time 1h~30h.
Graphene oxide has huge specific surface area, and a large amount of active groups are contained on its surface, can form the water of high stable Dissolubility colloid, there is higher adsorption capacity.It is combined in addition, graphene oxide is more easy to scale compared to CNT, it is made Standby raw material is nature graphite, and aboundresources, it is relatively low that scale is combined to cost.Therefore, fatty amine is removed using graphene oxide With very big advantage.
Graphene oxide has the characteristics of specific surface area is big, surface oxygen functional group is more and surface electronegativity is high, this hair The bright effective absorption realized using these features to fatty amine.Meanwhile the absorption induced oxidation graphene interface of fatty amine is hydrophobic, The graphene oxide Hydrophobic aggregation of suitable air-flotation process is formd, the recovery of graphene oxide is realized using Bubble-floating Method, is next Step regeneration is prepared.
Compared with prior art, technical scheme has the advantages that：
The present invention can effectively in Mineral Processing Industry sort oxide ore after remaining fatty amine remove, substantially reduce by Adverse effects of the floating agent remnants to sorting index in backwater；Meanwhile the flotation in the beneficiation wastewater discharged to needs is residual Remaining medicament is removed, and reduces adverse effect of the waste discharge to environment, to preserving the ecological environment, promotes sustainable economic development There is important social effect.
Graphene oxide used in the present invention is using cheap and rich reserves graphite as raw material, using maturation Hummer methods prepare graphene oxide suspension, can be directly used for removing fatty amine, it is not necessary to drying and scattered mistake Journey, shorten preparation and application flow, improve absorption property, low-cost industrial can prepare well, and have good Prospects for commercial application.
Graphene oxide fatty amine scavenger used in the present invention easily realizes the extensive separation of solid and liquid of low cost.Aoxidize stone Black alkene fatty amine scavenger adsorption reaction is completed, and fatty amine is hydrophobic by induced oxidation graphene interface, forms at suitable air supporting The graphene oxide Hydrophobic aggregation of reason, the separation of graphene oxide and purified water, the removing of air supporting recovery are realized using Bubble-floating Method Agent for regenerating in next step.Described above is only the general introduction of technical solution of the present invention, in order to better understand the skill of the present invention Art means, and being practiced according to the content of specification, and in order to allow the above and other purpose of the present invention, feature and excellent Point can become apparent, and below in conjunction with preferred embodiment, describe in detail as follows.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, the accompanying drawing of embodiment will be simply situated between below Continue.
Fig. 1 (a) is the AFM 2D afm images of graphene oxide；
Fig. 1 (b) is altitude profile figure corresponding to the atomic force microscopy diagram of graphene oxide；
Fig. 2 is removing dynamics of the graphene oxide to lauryl amine at 25 DEG C；
Fig. 3 is lauryl amine adsorption capacity of the graphene oxide to various concentrations under different temperatures；
Fig. 4 is the air supporting rate of recovery of graphene oxide after being acted on various concentrations lauryl amine solution；
Fig. 5 (a) is the outward appearance of graphene oxide suspension before air supporting under different lauryl amine initial concentrations；
Fig. 5 (b) is the outward appearance of air supporting rear oxidation graphene suspension under different lauryl amine initial concentrations.
Embodiment
The following detailed description of the present invention embodiment, its as part of this specification, by embodiment come Illustrate the principle of the present invention, other aspects of the present invention, feature and its advantage will become apparent by the detailed description.
Case study on implementation 1：
Present case illustrates the preparation method of graphene oxide suspension.
1) 1.0g aphanitic graphites are weighed and prepare graphite oxide, the graphite oxide prepared first is carried out to pickling in water Wash, finally use centrifuge again.
2) graphite oxide after centrifugation is dried 48 hours with vacuum freezing drying oven, dried graphite oxide is worn into Powder.
3) the 0.2g graphene oxide powders weighed are dispersed in 300mL water with FLUKO high shear dispersions mixer.
4) graphite oxide solution is peeled off with Cole Parmer (750W, 20KHz) ultrasonic cell disruptor 9min, amplitude controlling is 30%.
5) suspension after stripping is centrifuged 20 minutes under 4000r/min rotating speeds, supernatant liquor is graphene oxide Suspension, its concentration are 0.385g/L.
6) product detection：Shown in atomic force microscopy figure such as Fig. 1 (a) and Fig. 1 (b) of graphene oxide.Fig. 1 (a) is visible, The solid colour of most of stannic oxide/graphene nano piece, illustrate that its thickness approaches；Fig. 1 (b) is visible, stannic oxide/graphene nano piece Thickness is in 1.1nm, in the thickness range of monolithic layer.It can be seen that graphene oxide has been successfully prepared it.
Case study on implementation 2：
Present case illustrates the rate of adsorption of graphene oxide adsorbent.
1) the lauryl amine waste water that concentration is 200mg/L, the object as processing are taken.
2) graphene oxide suspension (10mL) prepared in case 1 and 200mg/L lauryl amine waste water (40mL) are existed Mixed in conical flask.
3) conical flask is put on oscillator, at a temperature of 25 DEG C of adsorption reactions, vibrated under rotating speed 150rpm, adsorbing and removing Time is respectively 0.25h, 1.5h, 3h, 5h, 9h, 11h, 21h and 24h.
4) conical flask that adsorption reaction is completed is taken out from oscillator, filtered using the filter that aperture is 0.22 micron Graphene oxide suspension, the scavenging solution after adsorption treatment is obtained, then its lauryl amine is surveyed with ultraviolet specrophotometer and is purifying Residual concentration in liquid.
5) according to formula：The adsorbance of graphene oxide is calculated as follows：Calculate graphene oxide Adsorbance.Wherein, qe(g·g-1) represent the equilibrium adsorption capacities of graphene oxide adsorbent, coAnd ce(mg·L-1) represent ten Residual concentration after the initial concentration and adsorption equilibrium of diamines, V (L) represent suspension vol, and m (g) represents graphene oxide Removing dynamics of the graphene oxide to lauryl amine is as shown in Figure 2 at .25 DEG C of quality.
The case can illustrate that the speed of graphene oxide adsorbing and removing lauryl amine is very fast, close to absorption during 0.25h Balance can be fully achieved in balance, 3h.
Case study on implementation 3：
Present case illustrates the influence of temperature and lauryl amine concentration to the adsorption capacity of graphene oxide adsorbent.
1) it is 0mg/L, 40mg/L, 80mg/L, 120mg/L, 160mg/L, 200 mg/L, 240mg/L, 280mg/ to take concentration L, 320mg/L, 360mg/L, 400mg/L lauryl amine waste water, the object as processing.
2) graphene oxide suspension (10mL) prepared in case 1 and 200mg/L lauryl amine waste water (40mL) are existed Mixed in conical flask.
3) conical flask is put on oscillator, at a temperature of 25 DEG C, 35 DEG C, 45 DEG C of adsorption reactions, vibrates rotating speed 150rpm Under, the adsorbing and removing time is 24h.
4) conical flask that adsorption reaction is completed is taken out from oscillator, filtered using the filter that aperture is 0.22 micron Graphene oxide suspension, the scavenging solution after adsorption treatment is obtained, then its lauryl amine is surveyed with ultraviolet specrophotometer and is purifying Residual concentration in liquid.
5) according to formula：The adsorbance of graphene oxide is calculated as follows：Calculate graphene oxide Adsorbance.Wherein, qe(g·g-1) represent the equilibrium adsorption capacities of graphene oxide adsorbent, coAnd ce(mg·L-1) represent ten Residual concentration after the initial concentration and adsorption equilibrium of diamines, V (L) represent suspension vol, and m (g) represents graphene oxide Quality.Under different temperatures, graphene oxide is as shown in Figure 3 to the lauryl amine adsorption capacity of various concentrations.
The case can illustrate that graphene oxide is very big to the adsorption capacity of lauryl amine, when lauryl amine initial concentration is 400mg/L, when adsorption reaction temperature is 45 DEG C, graphene oxide is to the adsorption capacity of lauryl amine up to 1.8g/g.Temperature carries Height, adsorption capacity of the graphene oxide to lauryl amine can be improved.
Case study on implementation 4：
Present case illustrates under different lauryl amine initial concentrations that Bubble-floating Method reclaims graphene oxide adsorbent effect.
1) it is 0mg/L, 40mg/L, 80mg/L, 120mg/L, 160mg/L, 200 mg/L, 240mg/L, 280mg/ to take concentration L, 320mg/L, 360mg/L, 400mg/L lauryl amine waste water, the object as processing.
2) graphene oxide suspension (10mL) prepared in case 1 and 200mg/L lauryl amine waste water (40mL) are existed Mixed in conical flask.
3) conical flask is put on oscillator, at a temperature of 25 DEG C of adsorption reactions, vibrated under rotating speed 150rpm, adsorbing and removing Time is 24h.
4) conical flask that adsorption reaction is completed is taken out from oscillator, now obtains the graphite oxide for having adsorbed fatty amine Alkene suspension, graphene oxide are converted into the floc sedimentation of hydrophobization simultaneously.
5) graphene oxide suspension after adsorption reaction is poured into mechanical agitation type flotation cell, is in flotation device rotating speed Under 1900rpm, aeration quantity 1400m3/m2Min, air supporting time are under 5min, enter promoting the circulation of qi to graphene oxide hydrophobization floc sedimentation Float back into receipts.It is finally obtained the graphene oxide after adsorption reaction and is stripped of the purified water of fatty amine.Different lauryl amines are initial Under concentration, the rate of recovery of graphene oxide adsorbent is as shown in Figure 4.Under different lauryl amine initial concentrations, the front and rear oxidation stone of air supporting The outward appearance contrast of black alkene suspension is as shown in Figure 5.
The case can illustrate that Bubble-floating Method is very high to the organic efficiency of graphene oxide.From fig. 4, it can be seen that work as lauryl amine Initial concentration when being 40mg/L, the rate of recovery of the graphene oxide adsorbent after adsorption reaction is close to 100%.Fig. 5 (a) is not With under lauryl amine initial concentration, the outward appearance of graphene oxide suspension before air supporting；Fig. 5 (b) be different lauryl amine initial concentrations under, The outward appearance of air supporting rear oxidation graphene suspension.From Fig. 5 (b), non-oxidation graphene is present in the purified water after air supporting, This had both solved the problems, such as the recovery of graphene oxide, can also obtain the measured purified water of matter.
The present invention makes full use of the huge specific surface area of graphene oxide, numerous surface oxygen functional groups and high surface (when lauryl amine initial concentration is 400mg/L, adsorption reaction temperature is 45 DEG C for efficient absorption removing of the electronegativity realization to fatty amine When, graphene oxide is to the adsorption capacity of lauryl amine up to 1.8g/g), meanwhile, the absorption of fatty amine can induce graphene oxide Surface hydrophobicity, the complete recovery of the graphene oxide after absorption can be realized using Bubble-floating Method.The present invention can be effectively to Mineral Processing Industry Residual fat amine after middle sorting oxide ore is removed, and substantially reduces in backwater flotation Residuals to the unfavorable of sorting index Influence；Meanwhile the Residuals in the beneficiation wastewater discharged to needs remove, unfavorable shadow of the waste discharge to environment is reduced Ring, to preserving the ecological environment, promote sustainable economic development to have important social effect.
Each raw material cited by the present invention, and bound, the section value of each raw material of the present invention, and technological parameter Bound, the section value of (such as temperature, time) can realize the present invention, embodiment numerous to list herein.
Described above is the preferred embodiment of the present invention, can not limit the right model of the present invention with this certainly Enclose, it is noted that for those skilled in the art, under the premise without departing from the principles of the invention, may be used also To make some improvement and variation, these are improved and variation is also considered as protection scope of the present invention.

Claims (11)

  1. A kind of 1. graphene oxide fatty amine scavenger, it is characterised in that：Graphene oxide suspension comprising 0.1~5g/L.
  2. 2. graphene oxide fatty amine scavenger as claimed in claim 1, it is characterised in that：Described graphene oxide suspends Liquid is to prepare gained graphene oxide suspension using Hummer methods.
  3. 3. graphene oxide fatty amine scavenger as claimed in claim 2, it is characterised in that：Described Hummer methods prepare oxygen Graphite alkene suspension, is comprised the following steps：
    Step 1: preparing graphite oxide using native graphite, the graphite oxide prepared first is carried out to pickling and washed again, again finally Centrifugation；
    Step 2: by the graphite oxide vacuum freeze drying 24-72 hours after centrifugation, by dried graphite oxide grinds End；
    Step 3: graphite oxide powder is dispersed in water；
    Step 4: carrying out ultrasound to graphite oxide solution peels off 5-15min；
    Step 5: the suspension after stripping is centrifuged, it is graphene oxide fatty amine scavenger to take supernatant liquor.
  4. 4. graphene oxide fatty amine scavenger as claimed in claim 3, it is characterised in that：In the step 1, natural stone Ink is one kind in crystalline flake graphite, block graphite or aphanitic graphite.
  5. 5. graphene oxide fatty amine scavenger as claimed in claim 3, it is characterised in that：In the step 3, stone is aoxidized Mo Yushui is according to 0.6-1.2g：1L ratio mixing.
  6. 6. graphene oxide fatty amine scavenger as claimed in claim 3, it is characterised in that：The obtained graphene oxide Graphene oxide concentration is 0.1~5g/L in fatty amine scavenger.
  7. 7. a kind of application process using graphene oxide fatty amine scavenger, it is characterised in that comprise the following steps：
    S1 prepares graphene oxide suspension using native graphite as raw material, using Hummer methods；
    S2 takes the waste water of fatty amine, the object as processing；
    S3 graphene oxide suspensions mix with waste water；
    S4 vibrates the mixed liquor obtained by S3, adsorbing and removing；
    S5 stirs the graphene oxide suspension after adsorption reaction, flotation, and air supporting is carried out to graphene oxide hydrophobization floc sedimentation Recovery, obtain the graphene oxide after adsorption reaction and be stripped of the purified water of fatty amine.
  8. 8. the application process of graphene oxide fatty amine scavenger is used as claimed in claim 7, it is characterised in that：Step S1 Described native graphite is one kind in crystalline flake graphite, block graphite or aphanitic graphite.
  9. 9. the application process of graphene oxide fatty amine scavenger is used as claimed in claim 7, it is characterised in that：Described in S2 Fatty amine be primary amine, secondary amine and tertiary amine and polyamines of the carbon chain lengths in the range of C8-C22 in one kind, the fatty amine Concentration is 10~5000mg/L.
  10. 10. the application process of graphene oxide fatty amine scavenger is used as claimed in claim 7, it is characterised in that：S3 institutes The graphene oxide suspension and the volume ratio 1%~50% of waste water stated.
  11. 11. the application process of graphene oxide fatty amine scavenger is used as claimed in claim 7, it is characterised in that：S4 institutes The adsorption reaction condition stated is 5 DEG C~40 DEG C, oscillator rotating speed 50r/min~300r/min of adsorption temp, the adsorbing and removing time 1h~30h.
CN201710519510.3A 2017-06-30 2017-06-30 Graphene oxide fatty amine remover and application method thereof Active CN107352661B (en)

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Publication number Priority date Publication date Assignee Title
CN101973620A (en) * 2010-09-21 2011-02-16 上海大学 Method for removing heavy metal ions in water by using graphene oxide sheet
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Publication number Priority date Publication date Assignee Title
CN101973620A (en) * 2010-09-21 2011-02-16 上海大学 Method for removing heavy metal ions in water by using graphene oxide sheet
US20120168383A1 (en) * 2010-12-29 2012-07-05 Korea Institute Of Science And Technology Graphene-iron oxide complex and fabrication method thereof
CN102153075A (en) * 2011-03-22 2011-08-17 桂林理工大学 Method for synthesizing graphene oxide by ultrasonic assistance Hummers method

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Title
谢昆: "《纳米技术在水污染控制中的应用》", 30 June 2014, 武汉：武汉大学出版社 *

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