CN107349905A - The method that a kind of nitrogen co-doped magnetic carbon material of fluorine removes hexavalent chromium in industrial wastewater - Google Patents
The method that a kind of nitrogen co-doped magnetic carbon material of fluorine removes hexavalent chromium in industrial wastewater Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid 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
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid 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
- B01J20/027—Compounds of F, Cl, Br, I
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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Abstract
The invention discloses the method that a kind of nitrogen co-doped magnetic carbon material of fluorine removes hexavalent chromium in industrial wastewater.This method comprises the following steps：（1）The pH value of the industrial wastewater containing hexavalent chromium is adjusted, adds the nitrogen co-doped magnetic carbon material of solid absorbent fluorine, forms mixing suspension；（2）To step（1）Gained mixing suspension heats, and is ultrasonically treated；After supersound process terminates, solid absorbent, the waste water after discharge processing are separated and recovered.Reaction temperature of the present invention is relatively low, and processing time is short, flow is simple, not only reduces the energy consumption in adsorption process, also improves the efficiency of absorption, saves the time.The present invention can be directly separated by filtration using the nitrogen co-doped magnetic carbon material of fluorine as adsorbent with waste water solution；The raw material for preparing the adsorbent simultaneously has wide material sources, and adsorption activity is higher, easily separated, cheap, corrosion-free and environment-friendly, and stability is good, the advantages that can be recycled.
Description
Technical field
The present invention relates to the improvement field of the waste water containing hexavalent chromium, and in particular to a kind of nitrogen co-doped magnetic carbon materials of fluorine
The method that material removes hexavalent chromium in industrial wastewater.
Background technology
The quickening of social modernization's process so that problem of environmental pollution is growed in intensity, and the water pollution of wherein earth surface is asked
Topic has become international much-talked-about topic.Contained heavy metal ion species is got over concentration in the sewage that modern industry causes to discharge
Come more, such as chromium, mercury, cadmium, lead and arsenic [Journal of Hazardous materials, 2009,161 (2-3):1103-
1108].Wherein, hexavalent chromium is a kind of common hypertoxic pollutant.And it has larger dissolubility in aqueous, and have
Very strong mobility, thus to the survival effect of environment and the mankind it is huge [Environmental Science＆Technology,
2010,44(16):6202-6208].Environmental Protection Agency USA provides that top limit of the chromium ion in drinking water is 100 μ g/L
[Water Research,2007,41(10):2101-2108].For some existing at present problems, scientific research circle at present is
Some technologies are developed with heavy-metal ion removal, including cyaniding, chemical precipitation, chemical reduction method, ion exchange and reverse osmosis
Saturating method [Separation and Purification Technology, 2002,26 (2):137-146；Journal of
Hazardous materials,2009,167(1):260-267；Advances in Environmental Research,
2003,7(2):471-478；Journal of Hazardous materials,2003,97(1):49-57；Journal of
Hazardous materials,2009,170(2):1119-1124].But there is the defects of more obvious in these methods.
Recent studies have found that had a clear superiority using absorption method, relatively low and efficient [the ACS Applied Materials＆ of its cost
Interfaces,2013,5(3):598-604], it can more effectively remove heavy metal.
Magnetic carbon nano-composite material has been got over due to its excellent removing heavy metals ion energy and the characteristic being easily isolated
Paid attention to get over by educational circles.The preparation of magnetic carbon nano-composite material is usually to cross introducing magnetic gold in carbon material preparation process
Belong to salt (such as Fe), so as to assign its excellent magnetic, contribute to quick separating [the Journal of after absorption is completed
Materials Chemistry A,2015,3(18):9817-9825].Since last year, surface is carried out into magnetic carbon material
It is modified and adulterates and be applied to environmental treatment and is increasingly becoming a focus [Carbon 2016；109:640-649；Carbon
2017；115:503-514].Our research confirms that heteroatomic introducing can effectively adjust the surface electronic characteristic of adsorbent,
So as to strengthen the suction-operated of its heavy metal ion.The magnetic mesoporous carbon material of N doping has excellent remove as adsorbent
Chromium ion removal capacity, its adsorbance is reachable~2000mg/g [Carbon 2016；109:640-649].Meanwhile hetero atom is mixed
Miscellaneous magnetic carbon material has stronger metal removal ability, and its unit area is far above other undoped magnetic except chromium speed
Material.Accordingly, we can confirm that the magnetic carbon material of double base doping should have a more preferable absorption property, and this aspect is ground
Study carefully does not have precedent both at home and abroad at present.The nitrogen co-doped magnetic carbon material of fluorine that the present invention uses administers industrial wastewater weight for adsorbent
Metal ion does not have relevant report also at present, and this is also the maximum bright spot of the present invention.
Based on this, it is used to remove the hexavalent chromium in industrial wastewater using the nitrogen co-doped magnetic carbon material of fluorine, proposes
The method of hexavalent chromium in Adsorption industrial wastewater, the research method have not yet to see report in association area.
The content of the invention
Gone in view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of nitrogen co-doped magnetic carbon material of fluorine
Except the method for hexavalent chromium in industrial wastewater.This method passes through using the nitrogen co-doped magnetic carbon material of fluorine as solid absorbent
The hexavalent chromium being ultrasonically treated in absorption industrial wastewater, flow is simple, safe operation, to point of the hexavalent chromium in waste water
From efficiency high, and the easily separated recycling of solid absorbent after handling.
The purpose of the present invention is achieved through the following technical solutions.
The method that a kind of nitrogen co-doped magnetic carbon material of fluorine removes hexavalent chromium in industrial wastewater, including following step
Suddenly：
(1) pH value of the industrial wastewater containing hexavalent chromium is adjusted, adds the nitrogen co-doped magnetic of solid absorbent fluorine
Carbon material, form mixing suspension；
(2) mixing suspension obtained by step (1) is heated, and be ultrasonically treated；After supersound process terminates, separation and recovery
Solid absorbent, the waste water after discharge processing.
Further, in step (1), in the industrial wastewater containing hexavalent chromium, the concentration of hexavalent chromium is
0.001~1000mg/L.
Further, in step (1), the pH value of the industrial wastewater of the regulation containing hexavalent chromium is 1~11.
Further, in step (1), in the nitrogen co-doped magnetic carbon material of the fluorine, magnetic-doped particle is Fe, F's
Content is 0.1~5.0wt%, and N content is 1.0~5.0wt%, and Fe content is 0.1~3wt%.
Further, in step (1), the nitrogen co-doped magnetic carbon material of the fluorine passes through melamine, poly- inclined tetrafluoro second
Alkene and the pyrolysis of nine water ferric nitrate one-step method are prepared：
Take melamine, poly- inclined tetrafluoroethene and nine water ferric nitrates to be dispersed in alcohol solvent, dry, be subsequently placed into tubular type
In stove, it is incubated after heating up in a nitrogen atmosphere, insulation is down to room temperature after terminating, and takes out, obtains the nitrogen co-doped magnetic of the fluorine
Carbon material.
Further, the mass ratio of the gross mass and Ferric Chloride Hydrated of the melamine and poly- inclined tetrafluoroethene is
0.1~10:1.
Further, the mass ratio of the melamine and poly- inclined tetrafluoroethene is 0.1~5:1
Further, the drying is in 60~130 DEG C of drying.
Further, the speed of the heating is 10 DEG C/min.
Further, the insulation is to be incubated 1~4 hour at 650~900 DEG C.
Further, in step (1), the solid absorbent is 0.0001~100g/ relative to the concentration of industrial wastewater
L。
Further, in step (2), the heating is heated to temperature as 10~50 DEG C.
Further, in step (2), the power of the supersound process is 10~300W.
Further, in step (2), the frequency of the supersound process is 0.1~100KHZ.
Further, in step (2), the time of the supersound process is 0.01~20h.
After wastewater treatment terminates, the solid absorbent of recovery uses pH to be obtained for 9~14 alkaline aqueous solution cleaning and regeneration
Clean regenerated solids adsorbent, and reenter as solid absorbent in wastewater treatment next time.
Compared with prior art, the invention has the advantages that and beneficial effect：
(1) reaction temperature of the present invention is relatively low, and processing time is short, flow is simple, safe operation, not only reduces adsorption process
In energy consumption, also improve the efficiency of absorption, save the time.
(2) present invention is molten as adsorbent, adsorbent and waste water using the nitrogen co-doped magnetic carbon material sorbent activity of fluorine
Liquid can be directly separated by filtration；The nitrogen co-doped magnetic carbon material preparing raw material of fluorine has wide material sources simultaneously, and adsorbent adsorbs
Activity is higher, and easily separated, cheap, corrosion-free and environment-friendly, stability is good, the advantages that can be recycled.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment, but protection scope of the present invention is not limited to
In the scope of embodiment statement.
In following examples, the nitrogen co-doped magnetic carbon material of solid absorbent fluorine is with melamine, poly- inclined tetrafluoroethene
It is that the pyrolysis of raw material one-step method forms with nine water ferric nitrates, specifically comprises the following steps：
Take 2g melamines, 1g to gather the inclined water ferric nitrate of tetrafluoroethene and 6g nine to be dispersed in 200mL alcohol solvents, 110
Dry, be subsequently placed into tube furnace at DEG C, rise to 800 DEG C with 10 DEG C/min heating rate in a nitrogen atmosphere and holding 2 is small
When, then treat that temperature is down to room temperature, take out, obtain the nitrogen co-doped magnetic carbon material of fluorine.
In the nitrogen co-doped magnetic carbon material of the fluorine that is prepared, F content is 2.21wt%, and N content is
3.05wt%, Fe content are 1.34wt%.
Analysis to hexavalent chromium concentration before and after the processing uses colorimetric method, and standard curve used is Ce=3.8716A-
0.00039；Wherein, CeIt is the concentration of measured chromium solution, A is the absorption intensity of ultraviolet chromatogram.
The eliminating rate of absorption of measuring and calculating treatment effect uses equation below：
R%=(C0-Ce)/C0× 100% (1)
Wherein, C0And CeIt is corresponding chromium solution concentration before and after the processing respectively, unit mg/L.
In addition, adsorption capacity qe(mg/g) drawn according to below equation：
qe=(C0-Ce) × V/m × 100% (2)
Wherein V represents the volume of chromium solution, unit L；M represents the quality of solid absorbent, unit g.
Embodiment 1
(1) it is 7 by pH value, the industrial wastewater and fluorine nitrogen containing hexavalent chromium that hexavalent chromium concentration is 200mg/L
Magnetic carbon material (the 2.5g/L, relative to waste water of codope；In the nitrogen co-doped magnetic carbon material of fluorine, F content is
2.21wt%, N content are 3.05wt%, and Fe content is 1.34wt%) it is added in closed reactor and mixes, formed mixed
Close suspension；
(2) mixing suspension is heated to 30 DEG C, with the frequency processing of 200W power and 20KHZ in ultrasonic cleaning machine
After 0.17h, liquid-solid phase mixture is taken out from vial, is filtered, obtain the aqueous solution after solid absorbent and processing.
Colorimetrically analysing is carried out to the aqueous solution after processing, the clearance of hexavalent chromium is 92.2%, and adsorption capacity is
73.8mg/g。
Embodiment 2~5
(1) it is 7, the hexavalent chromium concentration industrial wastewater and fluorine nitrogen containing hexavalent chromium as shown in table 1 by pH value
Magnetic carbon material (the 2.5g/L, relative to waste water of codope；In the nitrogen co-doped magnetic carbon material of fluorine, F content is
2.21wt%, N content are 3.05wt%, and Fe content is 1.34wt%) it is added in closed reactor and mixes, formed mixed
Close suspension；
(2) mixing suspension is heated to 30 DEG C, with the frequency processing of 200W power and 20KHZ in ultrasonic cleaning machine
After 0.17h, liquid-solid phase mixture is taken out from vial, is filtered, obtain the aqueous solution after solid absorbent and processing.
Colorimetrically analysing is carried out to the aqueous solution after processing, the removal of hexavalent chromium the results are shown in Table 1.
Table 1
As shown in Table 1, the initial concentration of hexavalent chromium raises the magnetic carbon material nitrogen co-doped by fluorine is reduced in waste water
Adsorption rate；But the adsorption capacity of the nitrogen co-doped magnetic carbon material of fluorine is greatly improved simultaneously.
Embodiment 6~9
(1) industrial wastewater containing hexavalent chromium, the fluorine that be 7 by pH value, chromium ion concentration is 200mg/L are nitrogen co-doped
Magnetic carbon material (2.5g/L, relative to waste water；In the nitrogen co-doped magnetic carbon material of fluorine, F content is 2.21wt%, and N's contains
Measure as 3.05wt%, Fe content is 1.34wt%) it is added in closed reactor and mixes, form mixing suspension；
(2) mixing suspension is heated to 30 DEG C, surpassed in ultrasonic cleaning machine with the frequency of 200W power and 20KHZ
Sonication, processing time are as shown in table 2；After supersound process terminates, liquid-solid phase mixture is taken out from vial, is filtered,
Obtain the aqueous solution after solid absorbent and processing.
Colorimetrically analysing is carried out to the aqueous solution after processing, the removal of hexavalent chromium the results are shown in Table 2.
Table 2
As shown in Table 2, the extension of sonication treatment time is advantageous to improve the nitrogen co-doped magnetic carbon material of fluorine to Cr VI
The adsorption rate of ion, while the magnetic carbon material for making fluorine nitrogen co-doped is greatly improved to the adsorption capacity of hexavalent chromium.
Embodiment 10~13
(1) it is 7 by pH value, the industrial wastewater and fluorine nitrogen containing hexavalent chromium that hexavalent chromium concentration is 320mg/L
The magnetic carbon material of codope, which is added in closed reactor, to be mixed, the addition such as table of the nitrogen co-doped magnetic carbon material of fluorine
(relative to waste water shown in 3；In the nitrogen co-doped magnetic carbon material of fluorine, F content is 2.21wt%, and N content is
3.05wt%, Fe content are 1.34wt%), form mixing suspension；
(2) mixing suspension is heated to 30 DEG C, when in ultrasonic cleaning machine with 200W power and 20KHZ frequency processing
Between 0.17h, from vial take out liquid-solid phase mixture, filtered, obtain solid absorbent and processing after the aqueous solution.
Colorimetrically analysing is carried out to the aqueous solution after processing, the removal of hexavalent chromium the results are shown in Table 3.
Table 3
As shown in Table 3, the addition concentration of the nitrogen co-doped magnetic carbon material of fluorine, which improves, is advantageous to improve to hexavalent chromium
Adsorption rate, but at the same time, the nitrogen co-doped magnetic carbon material of fluorine to the unit mass adsorption capacity of hexavalent chromium progressively
Decline, be not engaged in adsorbing because unnecessary avtive spot be present.
Embodiment 14~17
(1) it is industrial wastewater containing hexavalent chromium and fluorine that hexavalent chromium concentration is 1000mg/L is nitrogen co-doped
Magnetic carbon material (2.5g/L, relative to waste water；In the nitrogen co-doped magnetic carbon material of fluorine, F content is 2.21wt%, and N's contains
Measure as 3.05wt%, Fe content is 1.34wt%) it is added in closed reactor and mixes, regulation pH value is to as shown in table 4
Value, formed mixing suspension；
(2) mixing suspension is heated to 30 DEG C, when in ultrasonic cleaning machine with 200W power and 20KHZ frequency processing
Between 0.17h, from vial take out liquid-solid phase mixture, filtered, obtain solid absorbent and processing after the aqueous solution.
Colorimetrically analysing is carried out to the aqueous solution after processing, the removal of hexavalent chromium the results are shown in Table 4.
Table 4
As shown in Table 4, the performance impact of the pH value of the waste water magnetic carbon material nitrogen co-doped to fluorine is larger, in slant acidity body
In system, the nitrogen co-doped magnetic carbon material of fluorine improves to the absorption property of hexavalent chromium with the reduction of pH value, and in alkalescence
In system, the nitrogen co-doped magnetic carbon material of fluorine proposes reduction with the raising of pH value to the absorption property of hexavalent chromium.
Embodiment 18~22
(1) it is industrial wastewater containing hexavalent chromium and fluorine that hexavalent chromium concentration is 200mg/L is nitrogen co-doped
Magnetic carbon material (2.5g/L, relative to waste water；In the nitrogen co-doped magnetic carbon material of fluorine, F content is 2.21wt%, and N's contains
Measure as 3.05wt%, Fe content is 1.34wt%) it is added in closed reactor and mixes, regulation pH value is 7, forms mixing
Suspension；
(2) mixing suspension temperature is heated to value as shown in table 5, in ultrasonic cleaning machine with 200W power and
20KHZ frequency processing time 0.17h, from vial take out liquid-solid phase mixture, filtered, obtain solid absorbent and
The aqueous solution after processing.
Colorimetrically analysing is carried out to the aqueous solution after processing, the removal of hexavalent chromium the results are shown in Table 5.
Table 5
As shown in Table 5, the performance impact of the treatment temperature of the waste water magnetic carbon material nitrogen co-doped to fluorine is larger, with place
The rising of temperature is managed, the nitrogen co-doped magnetic carbon material of fluorine steps up to the absorption property of hexavalent chromium.
Embodiment 23~27
(1) it is industrial wastewater containing hexavalent chromium and fluorine that hexavalent chromium concentration is 200mg/L is nitrogen co-doped
Magnetic carbon material (2.5g/L, relative to waste water；In the nitrogen co-doped magnetic carbon material of fluorine, F content is 2.21wt%, and N's contains
Measure as 3.05wt%, Fe content is 1.34wt%) it is added in closed reactor and mixes, regulation pH value is 7, forms mixing
Suspension；
(2) mixing suspension temperature is heated to 30 DEG C, with the power and 20KHZ frequency in table 6 in ultrasonic cleaning machine
Rate processing time 0.17h, liquid-solid phase mixture is taken out from vial, is filtered, after obtaining solid absorbent and processing
The aqueous solution.
Colorimetrically analysing is carried out to the aqueous solution after processing, the removal of hexavalent chromium the results are shown in Table 6.
Table 6
As shown in Table 6, the performance impact of the sonification power of the waste water magnetic carbon material nitrogen co-doped to fluorine is larger, with
The rising of sonification power, the nitrogen co-doped magnetic carbon material of fluorine steps up to the absorption property of hexavalent chromium.
Embodiment 28~32
(1) it is industrial wastewater containing hexavalent chromium and fluorine that hexavalent chromium concentration is 200mg/L is nitrogen co-doped
Magnetic carbon material (2.5g/L, relative to waste water；In the nitrogen co-doped magnetic carbon material of fluorine, F content is 2.21wt%, and N's contains
Measure as 3.05wt%, Fe content is 1.34wt%) it is added in closed reactor and mixes, regulation pH value is 7, forms mixing
Suspension；
(2) mixing suspension temperature is heated to 30 DEG C, in ultrasonic cleaning machine with 200W power and table 7 shown in ultrasound
Frequency processing time 0.17h, liquid-solid phase mixture is taken out from vial, is filtered, after obtaining solid absorbent and processing
The aqueous solution.
Colorimetrically analysing is carried out to the aqueous solution after processing, the removal of hexavalent chromium the results are shown in Table 7.
Table 7
As shown in Table 5, the performance impact of the supersound process frequency of the waste water magnetic carbon material nitrogen co-doped to fluorine is larger, with
The rising for being ultrasonically treated frequency, the nitrogen co-doped magnetic carbon material of fluorine steps up to the absorption property of hexavalent chromium.
Stability embodiment 33~37
(1) it is industrial wastewater containing hexavalent chromium and fluorine that hexavalent chromium concentration is 200mg/L is nitrogen co-doped
Magnetic carbon material (2.5g/L, relative to waste water；In the nitrogen co-doped magnetic carbon material of fluorine, F content is 2.21wt%, and N's contains
Measure as 3.05wt%, Fe content is 1.34wt%) it is added in closed reactor and mixes, regulation pH value is 7, forms mixing
Suspension；
(2) mixing suspension is heated to 30 DEG C, when in ultrasonic cleaning machine with 200W power and 20KHZ frequency processing
Between 0.17h, from vial take out liquid-solid phase mixture, filtered, obtain solid absorbent and processing after the aqueous solution；
(3) solid absorbent is alternately cleaned by 1mol/L sodium hydroxide solution (pH 14) and deionized water, dried
Afterwards, used next time；And the aqueous solution after handling carries out colorimetrically analysing, the removal effect of hexavalent chromium is calculated.Such as
This is recycled 5 times, and measure hexavalent chromium in waste water goes division result as shown in table 8.
Table 8
As shown in Table 8, reuse 5 times, hexavalent chromium removal efficiency changes less in the case where pH value is 7, says
The nitrogen co-doped magnetic carbon material of bright fluorine can recycle, so as to reduce the cost of adsorbent.
Claims (10)
1. the method that a kind of nitrogen co-doped magnetic carbon material of fluorine removes hexavalent chromium in industrial wastewater, it is characterised in that bag
Include following steps：
（1）The pH value of the industrial wastewater containing hexavalent chromium is adjusted, adds the nitrogen co-doped magnetic carbon materials of solid absorbent fluorine
Material, form mixing suspension；
（2）To step（1）Gained mixing suspension heats, and is ultrasonically treated；After supersound process terminates, solid is separated and recovered
Adsorbent, the waste water after discharge processing.
2. according to the method for claim 1, it is characterised in that step（1）In, the industrial wastewater containing hexavalent chromium
In, the concentration of hexavalent chromium is 0.001 ~ 1000 mg/L.
3. according to the method for claim 1, it is characterised in that step（1）In, the industry of the regulation containing hexavalent chromium
The pH value of waste water is 1 ~ 11.
4. according to the method for claim 1, it is characterised in that step（1）In, the nitrogen co-doped magnetic carbon material of the fluorine
In, magnetic-doped particle is Fe, and F content is 0.1 ~ 5.0 wt%, and N content is 1.0 ~ 5.0 wt%, and Fe content is 0.1 ~ 3
wt%。
5. according to the method for claim 1, it is characterised in that step（1）In, the nitrogen co-doped magnetic carbon material of the fluorine
Preparation comprise the following steps：By melamine, gather inclined tetrafluoroethene and nine water ferric nitrates and be dispersed in alcohol solvent, 60 ~
Dry, be subsequently placed into tube furnace at 130 DEG C, be warming up to 650 ~ 900 DEG C in a nitrogen atmosphere and be incubated 1 ~ 4 hour, insulation terminates
After be down to normal temperature, take out, obtain the nitrogen co-doped magnetic carbon material of fluorine；The melamine and the gross mass for gathering inclined tetrafluoroethene
Mass ratio with nine Ferric Chloride Hydrateds is（0.1~10）:1, the melamine and gather inclined tetrafluoroethene mass ratio be（0.1~
5）:1.
6. according to the method for claim 1, it is characterised in that step（1）In, the solid absorbent is relative to Industry Waste
The concentration of water is 0.0001 ~ 100 g/L.
7. according to the method for claim 1, it is characterised in that step（2）In, the heating be heated to temperature for 10 ~
50℃。
8. according to the method for claim 1, it is characterised in that step（2）In, the power of the supersound process is 10 ~ 300
W。
9. according to the method for claim 1, it is characterised in that step（2）In, the frequency of the supersound process for 0.1 ~
100 KHZ。
10. according to the method for claim 1, it is characterised in that step（2）In, the time of the supersound process is 0.01
~20h.
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| CN109019744A (en) * | 2018-08-07 | 2018-12-18 | 华南理工大学 | A kind of method of the molding carbon material Adsorption heavy metal ions in wastewater of nitrating |
| CN109012565A (en) * | 2018-08-07 | 2018-12-18 | 华南理工大学 | A kind of method of the magnetic carbon material Adsorption heavy metal ions in wastewater of nitrating |
| CN109499529A (en) * | 2018-11-01 | 2019-03-22 | 华东理工大学 | A kind of magnetic porous carbon material of N doping and its preparation method and application |
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