CN110180499A - A kind of preparation method of the magnetic carbon nano adsorber of efficient removal Cr VI - Google Patents

A kind of preparation method of the magnetic carbon nano adsorber of efficient removal Cr VI Download PDF

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Publication number
CN110180499A
CN110180499A CN201910434022.1A CN201910434022A CN110180499A CN 110180499 A CN110180499 A CN 110180499A CN 201910434022 A CN201910434022 A CN 201910434022A CN 110180499 A CN110180499 A CN 110180499A
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magnetic carbon
carbon nano
adsorbent
nano adsorber
removal
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CN201910434022.1A
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Chinese (zh)
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肇启东
宋晓俊
李新勇
石勇
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Dalian University of Technology
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Dalian University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229Compounds of Fe
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds
    • C02F2101/22Chromium or chromium compounds, e.g. chromates

Abstract

The invention belongs to water process and energy environment field of material technology, a kind of preparation method of the magnetic carbon nano adsorber of efficient removal Cr VI.One step carbonization green syt magnetic carbon nano adsorber is passed through as presoma using the melamine and iron chloride that are rich in carbon nitrogen.By the adsorbent be added there are also Cr VI aqueous solution in, removed from chromate waste water using constant temperature oscillation containing Cr VI.Adsorbent of the invention has many advantages, such as that preparation method is simple, low in cost, recycling performance is good, efficiently can quickly remove Cr VI, Cr VI removal efficiency is up to 96.77%.Specific test condition are as follows: chromate waste water hexavalent chromium initial concentration is 50mg/L, pH=2, time of contact 90min, and it is 700 DEG C that material, which prepares carburizing temperature,.

Description

A kind of preparation method of the magnetic carbon nano adsorber of efficient removal Cr VI
Technical field
The invention belongs to water process and energy environment field of material technology, and in particular to a kind of magnetic Nano carbon adsorbent Preparation and the method for efficiently removing Cr VI in water removal.
Background technique
In recent years, environmental pollution is serious threatens human health and sustainable development, wherein the industry containing heavy metal ion Sanitary wastewater is that heavy metal pollution is caused to endanger one of maximum pollution sources.Artificial source is considered as the main original of heavy metal Cause, while heavy metal ion can also be introduced into environment from natural geology.Heavy metal ion, because it is with toxicity and carcinogenicity, It is considered as the most harmful pollutant of underground water and surface water, constitutes a serious threat to the mankind and aquatile.
Cr VI is a kind of toxic heavy metal ion, from a wealth of sources, such as leather tanning, steel and iron manufacturing, the industry system such as plating Conduct industry and pesticides application, mining industry etc. are prevalent in surface water and groundwater in the form of trivalent chromium and Cr VI, Wherein the toxicity of Cr VI is higher by more than 100 times than trivalent chromium.Therefore, Cr in sewage (VI) is reduced to Cr (III), be fixed Change is very important.The World Health Organization provides that Cr (VI) ion concentration is up to 50 μ g/L in drinking water.U.S. environment is protected Shield office regulation, country-level drinking water total chrome must not exceed 100 μ g/L.Currently used for Cr (VI) ion skill in removal sewage Art has, cyaniding processing, electrochemical deposition method, hyperfiltration, ion-exchange, absorption method etc..Wherein absorption method is because of at low cost, effect The advantages that rate is high, without secondary pollution, is widely used.Traditional adsorbent mainly has metal phosphate, biological adsorption matter, boiling Stone, clay mineral, active carbon etc..Therefore, the technology for developing effective adsorbent removal Cr (VI) is the key that during sewage is repaired Problem.
Magnetic carbon material is gone because of the magnetic properties with high-specific surface area, high absorption capacity, easy reclaiming in heavy metal Except aspect rapidly develops.In the recent period, there is the electron donor that a variety of materials are restored as Cr (VI), such as Zero-valent Iron (ZVI), Fe3O4, Zeroth order aluminium (ZVA1), cellulose and nitrogenous compound.And and Fe3O4And Fe2O3Nuclear phase ratio, magnetic carbon wrap up ZVI with higher Cr (VI) restores removal ability and faster removal rate, because ZVI can restore for Cr (VI) provides more electronics.This Outside, carbon-coating can also prevent ZVI to be oxidized and dissolve in an acidic solution, increase the service life of nano material.In addition, Heteroatom doping Carbon adsorbent removal efficiency can be improved, hetero atom can effectively adjust the negative charge density and alkalinity of carbon surface, to promote gold Belong to the rate of adsorption of ion.Cr VI in waste water is gone containing magnetic carbon material adsorbent using nitrogen-doping preparation at present There is no report on being gone back except application.
Summary of the invention
The purpose of the present invention is using to provide the presoma of ZVI and Heteroatom doping, being synthesized by one step carbonization can be high Effect removes the magnetic carbon nanomaterial of Cr VI in water removal.
Melamine and iron chloride is used to pass through the green syt that a step is carbonized as presoma the present invention provides a kind of Method prepares magnetic carbon nanomaterial, is added the magnetic carbon material of preparation as adsorbent in the solution containing Cr VI, so Afterwards using the Cr VI contained in constant temperature oscillation removal solution.
A kind of preparation method of the magnetic carbon nano adsorber of efficient removal Cr VI, steps are as follows:
Step 1, ferric chloride hexahydrate and melamine that mass ratio is 2:1~3:1 are mixed in ethanol solution, to stir Mixing the speed that speed is 100 revs/min~200 revs/min and stirring is uniformly mixed it, then that mixed liquor is dry, with Afterwards in N2With 600~900 DEG C of 2~3h of calcining at constant temperature carbonization under environment;
Step 2, the resulting bulk carbide of step 1 is ground, gained powder using mass fraction be 37~60% it is dense Salt acid elution gives up supernatant after centrifuge separation, retain solidliquid mixture, is placed in 60~80 DEG C of vacuum oven dry 10~12 hours to get magnetic carbon nano adsorption agent material.
The carburizing temperature is 700 DEG C.
Beneficial effects of the present invention: magnetic carbon material in the method for the present invention has that adsorption efficiency is good, returns as adsorbent The advantages that high income and cyclicity are stablized, the method for the present invention efficiently can quickly remove the Cr VI in sewage, reduce except chromium at This, Cr VI removal efficiency is up to 96.90%.
Detailed description of the invention
Fig. 1 is that the Flied emission scanning electron of the magnetic carbon nano adsorber prepared under different carburizing temperatures in embodiment 1 is aobvious Micro mirror image.The magnetic carbon material (MCN600) prepared when (a) is 600 DEG C of carburizing temperature in figure, correspondingly, in figure (b) (c) (d) the magnetic carbon material (MCN700, MCN800 and MCN900) for preparing when be respectively carburizing temperature being 700,800,900 DEG C.
Fig. 2 is the X-ray diffraction spectrum of the magnetic carbon nano adsorber prepared under different carburizing temperatures in example 1 in embodiment Figure.2 θ are expressed as twice of the angle of diffraction in figure, and unit is degree (°).In figure A, B, C and D curve be respectively carburizing temperature be 600, 700,800 and 900 DEG C when the magnetic carbon material (MCN600, MCN700, MCN800 and MCN900) for preparing.Positioned at 37.5 ° and Diffraction maximum at 55.0 ° can correspond respectively to Fe3O4(311) and (511) crystal face;At 26.6 °, 44.7 ° and 45.0 ° Diffraction maximum is corresponding in turn to (002) in ZVI, (100) and (110) crystal face.
Fig. 3 is the intensity of magnetization test of the magnetic carbon nano adsorber prepared under different carburizing temperatures in example 1 in embodiment Result figure.A, B, C and D curve are respectively carburizing temperature in the figure magnetic carbon material for preparing when being 600,700,800 and 900 DEG C (MCN600, MCN700, MCN800 and MCN900).
Fig. 4 is excellent to the condition of the removal efficiency of Cr VI in solution for the magnetic carbon nano adsorber prepared in embodiment 1 Change figure.
Fig. 5 is that the circulation of Cr VI in the magnetic carbon nano adsorber processing waste water containing chrome prepared in evaluation embodiment 1 is steady Qualitative result figure.
Specific embodiment
To further illustrate the technical problem to be solved in the present invention, technical solution and advantage, below in conjunction with specific implementation Example is described in detail.Obviously, described embodiment is a part of example of the invention, instead of all the embodiments.Base Embodiment in invention, those of ordinary skill in the art without making creative work it is obtained it is all its His embodiment, shall fall within the protection scope of the present invention.
It illustrates, Cr VI is denoted as Cr (VI) in the present invention, magnetic carbon nano adsorber is denoted as MCNs, carbonization The material that temperature is prepared when being 600,700,800,900 DEG C is denoted as MCN600, MCN700, MCN800, MCN900 respectively.
Embodiment 1: comparative experiments
Respectively select phase homogenous quantities different carburizing temperatures prepare resulting magnetic carbon nano adsorption agent material (MCN600, MCN700, MCN800 and MCN900) carry out water in hexavalent chromium removal experimental study.The result shows that reaching adsorption equilibrium MCN700 has maximum adsorbance and adsorption rate, respectively 46.34mg/g and 71.21% afterwards;It is MCN600 (adsorbance later It is respectively 43.84mg/g and 66.63%) with adsorption rate.MCN800 is compared with adsorption rate with the adsorbance of MCN900 and is wanted much lower, Therefore carburizing temperature cannot be excessively high in material preparation process
The Flied emission scanning electron of the magnetic carbon nano adsorber (MCNs) of the different carburizing temperatures prepared in the present invention is aobvious Micro mirror image as shown in Figure 1, synthesis MCNs surface topography it is irregular, material surface piece when can be seen that from Fig. 1 (c) at 700 DEG C Shape carbon and tubulose carbon exist simultaneously;The X-ray diffractogram of the MCNs prepared in the present embodiment is as shown in Fig. 2, from map To as the temperature rises, there is Fe in material surface3O4With the characteristic peak of Zero-valent Iron, this show between the carbon period iron chloride and Melamine occurs chemical reaction and generates Zero-valent Iron abundant and Fe3O4, MCNs crystallinity is good.To manufactured in the present embodiment MCNs tests the intensity of magnetization by vibrating specimen magnetometer, as a result as shown in Figure 3.With the raising of carburizing temperature, material is satisfied It is also increased with it with the intensity of magnetization, illustrates that Fe in carbonisation (III) is more reduced to ZVI as the temperature rises, it is right Recycling after the absorption of later period material is more advantageous.When carburizing temperature is 900 DEG C, the intensity of magnetization of material is maximum, this is tied with XRD Fruit is also corresponding, i.e., the diffraction peak intensity of ZVI is maximum at 900 DEG C.
Embodiment 2: further, in order to enable the effect of hexavalent chromium is most in magnetic carbon adsorbent processing waste water containing chrome It is good, the influence of the initial pH of solution, time of contact, Cr (VI) ion initial concentration to processing waste water containing chrome is had studied, is considered Influence of the pH value of solution to material absorption property obtains the condition optimizing of pH value of solution, time of contact and Cr (VI) ion initial concentration Figure is as shown in Figure 4.
The initial pH of solution: taking 50mL concentration is that Cr (VI) solion of 50mg/L is placed in the conical flask of 100mL, is used The pH value of 1mol/L hydrochloric acid and 1mol/L sodium hydrate regulator solution is respectively 2,3,4,5,6,7,8, weighs 7 parts of 0.05g MCN700 sample is added to respectively in each solution, is stirred evenly.Fig. 4 (a) is the results show that acidic environment is conducive to Cr (VI) ion Removal, and in pH=2 removal rate reach maximum 96.77% because pH is smaller, magnetic carbon adsorbent surface protonated amino Degree is higher, and OH- concentration is lower in solution, and the probability that Cr oxidation anion is adsorbed is bigger.In condition optimizing experiment below Use the dichromic acid aqueous alkali of pH=2 as chromate waste water.
Cr (VI) ion initial concentration: Cr (VI) ion stock solution that concentration is 500mg/L is diluted to 20,50, 100,150,200mg/L are respectively pivoted in 100mL conical flask, and three parallel, pH=2, MCN700 adsorbent is arranged in each concentration Dosage be 0.05g, be placed in constant temperature oscillator, when oscillation is to adsorption equilibrium, certain volume supernatant taken to measure Cr VI Concentration probes into the effect of magnetic carbon material removal Cr VI, and as Fig. 4 (b) is shown: the equilibrium adsorption capacity of MCN700 is with initial dense The increase of degree first increases to be reduced afterwards, and the removal rate of Cr (VI) ion is gradually reduced, therefore Cr VI initial concentration is 50mg/ More efficient economy when L.It therefore, the use of Cr VI initial concentration is 50mg/L, the weight of pH=2 in condition optimizing experiment once Chromic acid aqueous solutions of potassium is as chromate waste water.
Time of contact;Fig. 4 (c) be shown time of contact be 20,40,60,90,120,150,180,210,240,300, When 360min, MCN700 material removes the effect of Cr VI, and optimal time of contact is 90min as can be seen from Figure.
Embodiment 3: cyclical stability experiment of the magnetic carbon material as Cr VI in adsorbent processing waste water containing chrome is evaluated.
Under identical adsorption conditions, 50mgMCN700 absorption is added in Cr (VI) solution that 50mL concentration is 50mg/L Agent is centrifugated after oscillation to adsorption equilibrium, liquid is discarded supernatant, using 0.05molL-1CaCl2Solution, adsorbent pass through MCN700 after desorption to achieve the effect that Cr (VI) ion is desorbed, then is added to chromium solution ibid by ultrasonic cleaning desorption 4h In adsorbed.Repeat 5 absorption-desorption steps.As a result as shown in figure 5, for the first time to Cr (VI) solution of 50mg/L Adsorption rate be 96.90%, after by 6 circulation absorption-desorption experiments, adsorption rate has dropped 11.61%, but still can say Bright MCN700 has stronger power of regeneration, has the advantages that stablize cycling and reutilization when treating wastewater.
Finally, it should be noted that the above examples are only used to illustrate the technical scheme of the present invention, rather than its limitations;Although Present invention has been described in detail with reference to the aforementioned embodiments, and those skilled in the art should natural sciences;It still may be used To modify to technical solution documented by current each embodiment or equivalent replacement of some of the technical features; And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and Range.

Claims (2)

1. a kind of preparation method of the magnetic carbon nano adsorber of efficiently removal Cr VI, which is characterized in that steps are as follows:
Step 1, ferric chloride hexahydrate and melamine that mass ratio is 2:1~3:1 are mixed in ethanol solution, to stir speed Degree is uniformly mixed it for 100 revs/min~200 revs/min of speed stirring, then that mixed liquor is dry, then exists N2With 600~900 DEG C of 2~3h of calcining at constant temperature carbonization under environment;
Step 2, the resulting bulk carbide of step 1 is ground, the concentrated hydrochloric acid that gained powder is 37~60% using mass fraction Washing, gives up supernatant after centrifuge separation, retain solidliquid mixture, dry 10 are placed in 60~80 DEG C of vacuum oven~ 12 hours to get magnetic carbon nano adsorption agent material.
2. preparation method according to claim 1, which is characterized in that the carburizing temperature is 700 DEG C.
CN201910434022.1A 2019-05-23 2019-05-23 A kind of preparation method of the magnetic carbon nano adsorber of efficient removal Cr VI Pending CN110180499A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN103933951A (en) * 2014-05-13 2014-07-23 农业部环境保护科研监测所 Method for preparing chitosan-based adsorbent for adsorbing hexavalent chromium
CN106076275A (en) * 2016-06-29 2016-11-09 山东农业大学 A kind of porous magnetic Cr VI adsorbent and preparation method thereof
CN107473467A (en) * 2017-08-23 2017-12-15 华南理工大学 A kind of method of hexavalent chromium in Adsorption industrial wastewater

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103240054A (en) * 2012-02-07 2013-08-14 华中师范大学 Nitrogen-enriched magnetic nano-carbon adsorbent, preparation method thereof and applications on analysis
CN103933951A (en) * 2014-05-13 2014-07-23 农业部环境保护科研监测所 Method for preparing chitosan-based adsorbent for adsorbing hexavalent chromium
CN106076275A (en) * 2016-06-29 2016-11-09 山东农业大学 A kind of porous magnetic Cr VI adsorbent and preparation method thereof
CN107473467A (en) * 2017-08-23 2017-12-15 华南理工大学 A kind of method of hexavalent chromium in Adsorption industrial wastewater

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Application publication date: 20190830