CN103663601B - A kind of method of graphene oxide colloid fractionation by adsorption low-concentration heavy metal ions - Google Patents
A kind of method of graphene oxide colloid fractionation by adsorption low-concentration heavy metal ions Download PDFInfo
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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Abstract
A kind of method of graphene oxide colloid fractionation by adsorption low-concentration heavy metal ions, utilize the screening feature of dialysis membrane and the performance of graphene oxide colloid strong adsorption heavy metal ion, graphene oxide colloid is encapsulated in dialysis tubing and puts into heavy metal ion solution, heavy metal ion quickly through dialysis membrane by efficient adsorption, realize separation and the enrichment of heavy metal ion, the graphene oxide of adsorbed ion is after acidic solution process, heavy metal ion can efficient desorption, simultaneous oxidation Graphene is renewable and recycle, because the graphene oxide in dialysis tubing cannot pass through dialysis tubing, do not enter by the aqueous solution adsorbed, avoid the secondary pollution of sorbent material, greatly reduce solid-liquid separation amount.The invention process is simple, loading capacity is large, speed is fast, administers heavy metal in water ionic soil fast, preserve the ecological environment to efficient, promotes that there is important social effect sustainable economic development aspect.
Description
Technical field
The invention belongs to resource reclaim and water treatment field, particularly the method for low-concentration heavy metal ions fractionation by adsorption.
Technical background
Along with global industryization development, create a large amount of industry and sanitary sewage, containing heavy metal element in these sewage, just enter rivers and lakes if unprocessed, significant damage will be produced to ecological and the mankind.Heavy metal refers generally to the metal of proportion more than 5, mainly contains about 45 kinds of gold and silver, copper, lead, zinc, nickel, cobalt, chromium, mercury, cadmium etc.Wherein human body is poisoned and maximum have 4 kinds: chromium, cadmium, lead, mercury, these heavy metals can not be decomposed in water, easily enrichment on food chain, is combined with other toxin and generates toxicity larger organism toxicity is amplified, and has a strong impact on the healthy of ecotope and people.There is ten hundreds of person in current China every year by the murder by poisoning of heavy metal, and heavy metal brings huge threat to the healthy of people.Due to heavy metal enters after food chain can enrichment in superior being body, once be obtained except death is difficult to leave food chain by biology, therefore, the harm of heavy metal is very far-reaching.The main path of biological uptake heavy metal is by the water body by heavy metal contamination, and will solve the most basic method of the harm of heavy metal to human body and ecotope is heavy metal in removing water body at all.But the concentration of heavy metal in water body is general all very low, the greatest limit concentration of country's water quality conventional index heavy metal cadmium, chromium, mercury and lead is respectively 0.005mg/L, 0.05mg/L, 0.001mg/L and 0.01mg/L, low-concentration heavy metal is not obvious to human body short-term hazard, but long-term hazards is but huge.Therefore, make full use of novel material, develop the adsorption separation technology technique of efficient green and solve a Heavy Metals in Waters harm difficult problem that is healthy to people and ecotope and be all face of crucial importance of international community and instant problem.
The method of existing separating low concentration metal ion has the precipitator method, extraction process, ion-exchange-resin process, membrane separation process, absorption method etc., and precipitator method water consumption is comparatively large, and need use precipitation agent, just can be discharged in environment and go after waste liquid needs adjust ph.The problems such as although extraction process enrichment efficiency is high, enrichment times is large, compares too little, and extraction agent solution loss is large, and the high and secondary pollution of cost is large also thoroughly do not solve.Ion exchange method has better development and application prospect than extraction process, this is because ion exchange method technique is simple, equipment close, adsorption efficiency is high, desorption and regeneration is easy, easy to operate, be easy to realize the feature such as industrialization and automatization, and the method generally need not inflammable, explosive, poisonous and hazardous organism, waste water output is few, be easy to process, there is good social environment benefit, but ion-exchanger price is costly, easily contaminated in use procedure.Membrane separation process has, good separating effect, consuming little energy, level of automation advantages of higher simple, easy to operate without phase-state change, normal-temperature operation, equipment, and the dual purpose of wastewater treatment and Footwall drift can be realized, but membrane sepn needs high-tension apparatus and needs regularly to clean film, cause facility investment large, working cost is high.For the metal ion solution of separation, enriching low-concentration, adopt absorption method to have low, simple to operate, the Be very effective of power consumption, environmental pollution is little, selectivity advantages of higher, but find efficient, environmental protection, inexpensive sorbent material and avoid the secondary pollution of sorbent material to be current adsorption method of separation key issue urgently to be resolved hurrily.
In recent years, due to graphene oxide specific surface area super large, rich surface is containing active group, the aqueous colloidal of high stability can be formed, particularly compared with carbon nanotube, graphene oxide is easier to the synthesis of mass-producing low cost, and do not need special oxidation introducing hydrophilic radical to improve metal biosorption [DLi, MBM ü ller, SGilje, etal.Nat.Nanotechnol., 2008, 3:101 – 105], therefore, graphite alkenyl nanometer materials is shown great attention to containing in heavy metal and organic waste water in process, carry out a large amount of research work [KL ü, GXZhao, XKWang.ChinSciBull, 2012, 57:1223 – 1234].The research of XKWang team finds that the graphene oxide of few number of plies is to such as Pb (II) [GXZhao, XMRen, X.Gao, etal.DaltonTrans., 2011, 40:10945 – 10952], Cd (II), Co (II) [GXZhao, JXLi, XMRen, etal.Environ.Sci.Technol., 2011, 45:10454 – 10462] and U (VI) [GXZhao, TWen, XYang, etal.DaltonTrans., 2012, 41:6182 – 6188] etc. many heavy metal ion have very strong adsorptive power, wherein 842mg/g is reached to the maximal absorptive capacity of Pb (II).In order to improve the absorption property of graphite alkenyl nanometer materials further, by adopting the means of various modification and compound, many new and effective graphene-based composite nano adsorbents continue to bring out.The problem of secondary pollution is caused owing to using graphite alkenyl nanometer materials fractionation by adsorption metal ion to there is the rear solid-liquid separation difficulty of absorption; the focus synthesis of the graphene-based composite nano materials of steering load magnetic nano-particle and the ionic adsorption again of research; the magnetic graphene mixture of synthesis such as V.Chandra carrys out As (III) in planar water and As (V); after absorption, As concentration is low to moderate 1ppb [VChandra; JPark; YChun; etal.ACSNano; 2010,4:3979 – 3986]; The Fe of the grafting beta-cyclodextrin modification on graphene oxide such as LLFan
3o
4the magnetic composite nano material of synthesis can Cr (VI) [LLFan in quick adsorption waste water, CNLuo, MSun, etal.J.Mater.Chem., 2012,22:24577 – 24583], solid-liquid separation can be realized easily under these magnetic graphene base adsorbent outside magnetic field effects, and ionic adsorption capacity is also improved.Although carried out a large amount of research work in graphite alkenyl nanometer materials process containing in heavy metal and organic waste water, so far there are no, and any research of combining for fractionation by adsorption heavy metal ion about graphite alkenyl nanometer materials and dialysis membrane is reported, research in the past mainly to improve absorption property and to improve application performance for guiding, studies its application in field of waste water treatment by the technique means such as modification and compound synthesizing new high-efficient graphite thiazolinyl composite Nano sorbing material.Current report utilize colloid sorbing material process waste water adsorption and enrichment metal ion to be wherein nearly all be dispersed in by sorbent material in waste water and directly contact with waste water, thus there is the problem of secondary pollution that sorbent material produces and the large even difficulty of solid-liquid separation amount.Although magnetic graphene base composite nano sorbent material is gathered by convenient realization of externally-applied magnetic field interaction energy; but the filtration through the large scale of construction under outside magnetic field must could realize solid-liquid separation, and magnetic compound particles synthesis technique is complicated, cost is high, be difficult to mass-producing practical application.
Summary of the invention
The object of the invention is propose a kind of efficient, quick, easy and do not produce secondary pollution by graphene oxide colloid fractionation by adsorption low-concentration heavy metal ions be separated method.Utilize the screening feature of dialysis membrane and the performance of graphene oxide colloid strong adsorption heavy metal ion, graphene oxide colloid is encapsulated in dialysis tubing, put into heavy metal ion solution, heavy metal ion can quickly through dialysis membrane by efficient adsorption, realize separation and the enrichment of heavy metal ion, adsorb saturated graphene oxide after acidic solution process, heavy metal ion can efficient desorption, simultaneous oxidation Graphene also can reprocessing cycle use, because the graphene oxide in dialysis tubing cannot pass through dialysis tubing, do not enter by the aqueous solution adsorbed, avoid the secondary pollution of sorbent material, greatly reduce solid-liquid separation amount.
Method of the present invention comprises the following steps.
(1) take natural flake graphite as raw material, adopt Hummer legal system for graphene oxide colloid, be mixed with the graphene oxide colloid of 0.1 ~ 2.0mg/ml.
(2) get proper volume graphene oxide colloid, after loading dialysis tubing sealing, put into the heavy metal ion aqueous solution be under static, vibration or supersound process state, heavy metal ion is by the absorption of dialysis membrane oxidized Graphene.
(3) dialysis tubing of the graphene oxide of heavy metal ion will have been adsorbed in step (2), put into be in static, vibration or supersound process state under the acidic solution being greater than 0.2M, heavy metal ion is from desorption graphene oxide, and graphene oxide colloid regenerates;
Step (2) dialysis tubing water molecules used, metal ion, small volume negatively charged ion can be quickly through, and graphene oxide sheet cannot pass through; Heavy metal ion solution upon adsorption refers to that its concentration is less than 500mg/L, and pH value is 5.00 ~ 12.00 containing one or more solution in cadmium, lead, mercury and chromium ion.
Acidic solution described in step (3) is nitric acid or hydrochloric acid.
The sorbent material of the present invention using graphene oxide colloid as low-concentration heavy metal ions in water, the graphene oxide specific surface area of two-dimensional nanostructure is large, a large amount of oxygen-containing functional group is had to exist, surface band negative charge, be sealed in dialysis tubing and do not disperse to enter by adsorbent solution, secondary pollution can not be caused, and the graphene oxide colloid of saturated adsorption heavy metal ion can regenerate and recycle easily.
The graphene oxide colloid that the present invention is used, adsorbed ion speed is fast, and capacity is large, renewablely recycles.
The present invention's graphene oxide used for raw material with natural flake graphite cheap and easy to get, adopts ripe Hummer legal system standby, has good low-cost industrial to prepare prospect and feasibility.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of prepared graphene oxide.As shown in Figure 1, obtained graphene oxide is the two-dimensional nanostructure of ultra-thin curling shape.
Fig. 2 is the atomic force microscopy of prepared graphene oxide.As shown in Figure 2, obtained micron order graphene oxide thickness only has 0.947nm, can infer that the number of plies is 1.
Fig. 3 is the infrared spectrogram of prepared graphene oxide.As shown in Figure 3, a large amount of oxygen-containing functional group that obtained graphene oxide contains.
Fig. 4 is the Raman spectrogram of prepared graphene oxide.As shown in Figure 4, D peak, G peak is consistent with the graphene oxide reported in document with 2D peak.
Fig. 5 is the XRD spectra of prepared graphene oxide, as shown in Figure 5, coincide with the characteristic diffraction peak of graphene oxide.
Fig. 6 is the mechanism figure that dialysis membrane assists lower graphene oxide adsorption/desorption ion, owing to there is the diffusion potential that ionic concn difference produces inside and outside dialysis membrane, and be dispersed in electronegative graphene oxide in dialysis tubing to the strong adsorption of positively charged ion, ion and small molecules can rapidly by the micropores of dialysis membrane, the wherein oxidized Graphene colloid absorption of heavy metal ion, two dimensional oxidation graphene film is then blocked in dialysis tubing due to the aperture being far longer than dialysis membrane, so just achieve the absorption of ion on dialysis tubing internal oxidition Graphene, efficiently solve ubiquitous sorbent material in adsorption separation technology and cause the problem of secondary pollution.When the dialysis tubing that the graphene oxide colloid having adsorbed a certain amount of heavy metal ion is housed puts into the acidic solution of proper concn, heavy metal ion again can desorption fast, thus achieves the separation of ion and the regeneration of enrichment and graphene oxide.
Embodiment
The present invention will be described further by following examples.
The Hummer method Preparation and characterization of graphene oxide colloid: take 5g natural flake graphite sheet, adds 120ml constant temperature in the vitriol oil of 0 DEG C, under constant temperature 0 DEG C of condition, add 2.5g SODIUMNITRATE, stir 30min, then add 20g potassium permanganate, then constant temperature 30 DEG C stirs 30min, add 300ml deionized water, control temperature is below 50 DEG C, after adding, 100 DEG C of insulation 20min, add the dilution of 20ml deionized water, drip 30% hydrogen peroxide again, glassy yellow is become to mixed solution, supersound process 15min, leave standstill 24 hours, outwell upper liquid, add volumetric concentration 1:10HCl, supersound process 30min, leave standstill 24 hours, outwell supernatant, add 200ml deionized water, supersound process 30min, leave standstill 10 hours, outwell supernatant, repeat with deionized water wash, layering is there is not to leaving standstill, loading dialysis tubing is put into deionized water and is dialysed, period each for some time changes a deionized water, until graphene oxide gel pH is close to 6.0, graphene oxide prepared by constant volume, the concentration of graphene oxide is demarcated by weighting method.Preparation graphene oxide adopt transmission electron microscope, atomic force microscope, infrared spectrometer, Raman spectrometer and X-ray diffractometer to characterize respectively, result respectively as Fig. 1, shown in 2,3,4 and 5.
Embodiment.
The mechanism (as shown in Figure 6) of lower graphene oxide absorption/desorb ions is assisted based on the relevant dialysis membrane of the present invention, the dialysis tubing of 10ml0.1mg/ml graphene oxide colloid 4 is equipped with, put into and respectively 45mlpH=6.00 is housed, concentration is 20 μ g/mlCr (VI), Pb (II), in 4 Erlenmeyer flasks of Cd (II) and Hg (II) solion, be placed in constant temperature water bath vibration groove, 30 DEG C of constant temperature oscillations are saturated to the absorption of graphene oxide colloid, get by adsorbent solution, with concentration of metal ions residual in atomic absorption spectroscopy determination solution, and calculate graphene oxide to Cr (VI) with minusing, Cd (II), the maximal absorptive capacity of Hg (II) and Pb (II), and make form 1.
Table 1 is for graphene oxide colloid described in embodiment 2 is to the maximal absorptive capacity data of Cr (VI), Pb (II), Cd (II) and Hg (II).The saturated extent of adsorption of graphene oxide to Cr (VI), Pb (II), Cd (II) and Hg (II) is 108mg/g, 786mg/g, 56mg/g and 616mg/g respectively.
Table 1. graphene oxide colloid to the maximum adsorption capacity of 4 heavy metal species ions (
q s )
| Ion | Cr(VI) | Pb(II) | Cd(II) | Hg(II) |
| Q( smg/g) | 108 | 786 | 56 | 616 |
Claims (1)
1. a method for graphene oxide colloid fractionation by adsorption low-concentration heavy metal ions, is characterized in that comprising the following steps:
(1) take natural flake graphite as raw material, adopt Hummer legal system for graphene oxide colloid, be mixed with the graphene oxide colloid of 0.1 ~ 2.0mg/ml, the pH value of described graphene oxide colloid is 6;
(2) get proper volume graphene oxide colloid, after loading dialysis tubing sealing, put into the heavy metal ion aqueous solution be under static, vibration or supersound process state, heavy metal ion is by the absorption of dialysis membrane oxidized Graphene;
(3) dialysis tubing of the graphene oxide of heavy metal ion will have been adsorbed in step (2), put into be in static, vibration or supersound process state under the acidic solution being greater than 0.2M, heavy metal ion is from desorption graphene oxide, and graphene oxide colloid regenerates;
Step (2) dialysis tubing water molecules used, metal ion, small volume negatively charged ion can be quickly through, and graphene oxide sheet cannot pass through; The heavy metal ion aqueous solution refers to that its concentration is less than 500mg/L, and pH value is 5.00 ~ 12.00 containing one or more solution in cadmium, lead, mercury and chromium ion;
Acidic solution described in step (3) is nitric acid or hydrochloric acid.
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| CN104772045B (en) * | 2015-03-23 | 2017-03-22 | 中国科学院生态环境研究中心 | Electrochemical selective membrane for removal of heavy metal ions in water, preparation method and application thereof |
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| CN108821381A (en) * | 2018-07-03 | 2018-11-16 | 苏州佰锐生物科技有限公司 | A kind of method of quick removal heavy metal in waste water mercury ion |
| CN109046294A (en) * | 2018-09-04 | 2018-12-21 | 苏州佰锐生物科技有限公司 | A kind of preparation method for the nano thin-film removing heavy metal in waste water mercury ion |
| CN109107537B (en) * | 2018-09-17 | 2021-03-19 | 济南大学 | Adsorbent for treating hexavalent chromium in neutral wastewater and preparation method thereof |
| CN109461984B (en) * | 2018-10-19 | 2022-06-07 | 浙江衡远新能源科技有限公司 | Method for recovering valuable metals in waste lithium ion batteries |
| CN109277090B (en) * | 2018-11-20 | 2021-07-02 | 江西省农业科学院农产品质量安全与标准研究所 | Method for simultaneously and rapidly adsorbing heavy metal ions of chromium, cadmium and lead |
| CN110745904A (en) * | 2019-10-12 | 2020-02-04 | 南京师范大学 | Test device and test method for removing heavy metal mercury in desulfurization wastewater |
| CN111239347A (en) * | 2020-03-27 | 2020-06-05 | 暨南大学 | Method for detecting desorption rate of organic matters in solid waste |
| CN113307326A (en) * | 2021-05-20 | 2021-08-27 | 江西善拓环境科技有限公司 | Preparation of tungsten-based oxide/carbon-based nano composite hydrosol and application of tungsten-based oxide/carbon-based nano composite hydrosol in wastewater treatment |
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| 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 |
| CN102617772A (en) * | 2012-04-01 | 2012-08-01 | 无锡格瑞恩环保科技有限公司 | Method for preparing polystyrene microspheres for heavy metal ion water treatment |
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