CN104045123B - Carboxylated magnetic oxygenated Graphene is utilized to remove cadmic method in waste water - Google Patents
Carboxylated magnetic oxygenated Graphene is utilized to remove cadmic method in waste water Download PDFInfo
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- CN104045123B CN104045123B CN201410327625.9A CN201410327625A CN104045123B CN 104045123 B CN104045123 B CN 104045123B CN 201410327625 A CN201410327625 A CN 201410327625A CN 104045123 B CN104045123 B CN 104045123B
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- magnetic oxygenated
- oxygenated graphene
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Abstract
The invention discloses one utilizes carboxylated magnetic oxygenated Graphene to remove cadmic method in waste water, said method comprising the steps of: get a certain amount of divalence cadmium waste water and adjust ph is 2.0 ~ 11.0 (is preferably 5.0 ~ 7.0, optimum is 6.0), a certain amount of carboxylated magnetic oxygenated Graphene is added in waste water, the carboxylated magnetic oxygenated Graphene dry weight of adding in often liter of waste water is 0.02g ~ 5g, be react 0 ~ 24h (most preferably being 1h ~ 6h) in the constant temperature oscillator of 50rpm ~ 300rpm at rotating speed, and to control temperature of reaction be 10 DEG C ~ 50 DEG C (optimum is 20 ~ 40 DEG C), after having reacted, carboxylated magnetic oxygenated Graphene is separated from solution, complete removal cadmic in waste water.The present invention has that cost is low, easy to operate, processing efficiency is high, is easy to the advantages such as Separation and Recovery.
Description
Technical field
The invention belongs to environment functional material and water treatment new technical field, particularly relate to the application of a kind of carboxylated magnetic oxygenated Graphene in process heavy metal wastewater thereby.
Background technology
Along with the development of the industries such as dyestuff, metallurgy, plating, mining, the heavy metal ion in entered environment gets more and more, and the environment such as the soil that the mankind depend on for existence, water body have been subjected to serious heavy metal contamination, and in aggravation trend.When heavy metal content has exceeded certain limit, the deterioration of the ecological environment and quality of agricultural product can be caused to decline, finally have a strong impact on the health of the mankind.Cadmium is as a heavy metal species, can produce respiratory tract and stimulate, long-term exposure can cause anosmia, gum macula lutea or gradually become yellow circle, cadmic compound is not easily by intestinal absorption, but can through breathing by body absorption, lodge in liver or kidney works the mischief, especially with the most obvious to kidney damage, also can cause osteoporosis and softening.Current industrial heavy metal ion-containing waste water mainly adopts chemical precipitation method and ion exchange method.Chemical precipitation method produces a large amount of mud in treating processes, easily causes secondary pollution.Ion exchange method costly, and regeneration there is certain difficulty.In addition, absorption method is emerging treatment process, but technology is ripe not enough.Conventional sorbent material has carbon fibre material, zeolite, clay mineral and some oxide compounds etc.In actual applications, due to reasons such as raw material sources are not abundant, adsorptive power is inadequate, the widespread use of these sorbent materials is limited.Therefore, prepare a kind of sorbent material that can address these problems to be of great immediate significance.
Graphene oxide is the product of powdered graphite after chemical oxidation and stripping, is single atomic shell, in oxidising process, many oxy radicals such as C-O-C, C-OH, C=O, COOH etc. is connected with graphite linings covalency.These functional groups can produce sequestering action as adsorption site and metal ion, but due to its wetting ability, are difficult to afterwards be separated from waste water in absorption.This problem is solved by magnetic oxygenated Graphene magnetic nano-particle load synthesized in surface of graphene oxide, but the puzzlement brought is in magnetic history, some adsorption sites of surface of graphene oxide are occupied by magnetic nano-particle, cause magnetic oxygenated Graphene adsorption site to reduce, adsorptive power also reduces.In order to improve its adsorptive power, just need to increase on its surface the adsorption site that heavy metal ion has stronger sequestering action.A lot of amino and carboxyl is carried on diethylenetriamine tetraacethyl surface, and heavy metal and organic pollutant can produce good tetra-inclusion complex, but it is as sorbent treatment heavy metal, are not easy to realize solid-liquid separation.Diethylene triamine pentacetic acid (DTPA) is formed matrix material by certain method grafting to magnetic oxygenated graphenic surface, adds the adsorption site of magnetic oxygenated Graphene, improve the adsorptive power of its heavy metal ion, and easily realize solid-liquid separation.Also carboxylated magnetic oxygenated Graphene is not applied to the precedent of cadmium wastewater process at present.
Summary of the invention
Technical problem to be solved by this invention is: the deficiency existed for prior art, provides the carboxylated magnetic oxygenated Graphene that utilizes that a kind of operational condition is simple, easy to implement, applied range, cost are low, efficiency is high to remove cadmic method in waste water.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is that one utilizes carboxylated magnetic oxygenated Graphene to remove cadmic method in waste water, said method comprising the steps of: get a certain amount of divalence cadmium waste water and adjust ph is 2.0 ~ 11.0 (is preferably 5.0 ~ 7.0, optimum is 6.0), a certain amount of carboxylated magnetic oxygenated Graphene is added in waste water, the carboxylated magnetic oxygenated Graphene dry weight of adding in often liter of waste water is 0.02g ~ 5g, be react 0 ~ 24h (most preferably being 1h ~ 6h) in the constant temperature oscillator of 50rpm ~ 300rpm at rotating speed, and to control temperature of reaction be 10 DEG C ~ 50 DEG C (optimum is 20 ~ 40 DEG C), after having reacted, carboxylated magnetic oxygenated Graphene is separated from solution, complete removal cadmic in waste water.
In technique scheme, described carboxylated magnetic oxygenated Graphene is obtained by following steps:
(1) by 1.0 ~ 5.0g graphite, 1.0 ~ 5.0gK
2s
2o
8, 1.0 ~ 5.0gP
2o
5with 1 ~ 20mLH
2sO
4in heating in water bath to 60 ~ 100 DEG C after mixing, add 0.2 ~ 1.0L ultrapure water after reaction 1 ~ 8h, after cooling, place 5 ~ 24h, remove residual acid with ultrapure water cleaning, 40 ~ 80 DEG C of vacuum-dryings, dried product is added the H that 80 ~ 150mL temperature is 0 ~ 10 DEG C
2sO
4in (95 ~ 98%), then add 1.0 ~ 5.0gNaNO
3, 5 ~ 25gKMnO
4, and the 1 ~ 8h that vibrates at 0 ~ 20 DEG C, then at 20 ~ 50 DEG C of reaction 1 ~ 5h, then add 0.1 ~ 0.5L water and ensure that temperature of reaction controls at 80 ~ 100 DEG C, continue vibration 2 ~ 10h, then add 0.4 ~ 1.0L water and 10 ~ 40mLH
2o
2(20 ~ 40wt%), vibrate under room temperature 1 ~ 4h, then uses HCl (5 ~ 20%) and water repeatedly to clean, then at 30 ~ 60 DEG C ultrasonic 1 ~ 3h, obtain the graphene oxide that concentration is 1 ~ 10g/L after constant volume;
(2) at room temperature, by the FeCl of 0.005 ~ 0.02mol
3with the FeSO of 0.002 ~ 0.01mol
4incorporate in 100 ~ 150mL ultrapure water, add in the graphene oxide solution described in 100 ~ 300mL step (1), adding rapidly 10 ~ 100mL ammoniacal liquor (massfraction is 30 ~ 90%) regulates pH to be 9 ~ 11, and under 70 ~ 100 DEG C of conditions Keep agitation 10 ~ 60min, solution is made to be cooled to room temperature, extremely neutral with ultrapure water cleaning again, obtain the magnetic oxygenated Graphene that concentration is 1 ~ 10g/L after constant volume;
(3) at room temperature, by the magnetic oxygenated graphene solution of the 1 ~ 10mg/mL of 500 ~ 2000mL of step (2) gained, at room temperature 5 ~ 60min is stirred;
(4) volumetric concentration that the diethylene triamine pentacetic acid (DTPA) taking 1 ~ 10g is dissolved in 10 ~ 50mL is 1:1 ammoniacal liquor, adds in the magnetic oxygenated Graphene of step (3) gained, stirred at ambient temperature 5 ~ 30min after dissolving;
(5) add 5 ~ 50mL quadrol toward the solution of step (4) gained rapidly, use clean water after being heated to 50 ~ 100 DEG C of reaction 1 ~ 10h, constant volume obtains the carboxylated magnetic oxygenated Graphene that concentration is 1 ~ 10g/L.
In technique scheme, in described waste water, the concentration of cadmium preferably controls 5 ~ 300mg/L (most preferably being 5 ~ 50mg/L).
Compared with prior art, the invention has the advantages that:
1. the carboxylated magnetic oxygenated Graphene used in method of the present invention, its raw material sources are extensive, and cheap, and main raw material Graphite Powder 99, Z 250, diethylene triamine pentacetic acid (DTPA) etc. are all conventional Chemicals;
2. carboxylated magnetic oxygenated Graphene is directly added in reactor and carry out absorption reaction, after having reacted, utilize magnet to realize solid-liquid separation.Whole treatment process cost is lower, operates more simply and easily implements, and is easy to, from the solution after process, carboxylated magnetic oxygenated Graphene is separated recycling;
3. method of the present invention effectively can process divalence cadmium waste water, and the improvement for heavy metal pollution in wastewater provides new approach.
Embodiment
Below with reference to specific embodiment, the present invention is described in further details.
Embodiment 1:
One is of the present invention utilizes carboxylated magnetic oxygenated Graphene to remove cadmic method in waste water, comprises the following steps:
1. the preparation of carboxylated magnetic oxygenated Graphene
(1) by 3.0g graphite, 2.5gK
2s
2o
8, 2.5gP
2o
5with 1 ~ 20mLH
2sO
4in heating in water bath to 60 ~ 100 DEG C after mixing, add 0.5L ultrapure water after reaction 4h, after cooling, place 12h, remove residual acid with ultrapure water cleaning, 60 DEG C of vacuum-dryings, dried product is added the H that 120mL temperature is 0 DEG C
2sO
4(98%) in, then 2.5gNaNO is added
3, 15gKMnO
4, and the 4h that vibrates at 20 DEG C, then at 35 DEG C of reaction 2h, then adds 250mL water and ensures that temperature of reaction controls at 90 DEG C, continue vibration 1h, then add 0.5L water and 20mLH
2o
2(30%), vibrate under room temperature 2h, then use HCl (mass concentration is 10%) and water repeatedly to clean, then at 50 DEG C ultrasonic 2h, obtain the graphene oxide that concentration is 5.2g/L after constant volume;
(2) at room temperature, by the FeCl of 0.01mol
3with the FeSO of 0.005mol
4incorporate in 120mL ultrapure water, add in the graphene oxide solution described in 200mL step (1), adding rapidly proper ammonia regulates pH to be 10, and under 85 DEG C of conditions Keep agitation 45min, solution is made to be cooled to room temperature, extremely neutral with ultrapure water cleaning again, obtain the magnetic oxygenated Graphene that concentration is 4.6g/L after constant volume;
(3) at room temperature, by the magnetic oxygenated graphene solution of the 1 ~ 10g/L of the 1200mL of step (2) gained, at room temperature 5 ~ 60min is stirred;
(4) volumetric concentration that the diethylene triamine pentacetic acid (DTPA) taking 3.0g is dissolved in 20mL is 1:1 ammoniacal liquor, adds in the magnetic oxygenated Graphene of step (3) gained, stirred at ambient temperature 10min after dissolving;
(5) add 18mL quadrol toward the solution of step (4) gained rapidly, use clean water after being heated to 80 DEG C of reaction 6h, after constant volume, obtain the carboxylated magnetic oxygenated Graphene that concentration is 2.9g/L.
2. pair divalence cadmium waste water processes
Configure the divalence cadmium waste water that 10 50mL concentration are 10mg/L, be respectively 2,3,4,5,6,7,8,9,10,11 by nitric acid or sodium hydroxide adjust ph.The carboxylated magnetic oxygenated Graphene prepared by aforesaid method adds in above-mentioned ten divalence cadmium waste waters, and the carboxylated magnetic oxygenated Graphene dry weight of adding in often liter of waste water counts 58mg.Reactor is placed in the vibration case that rotating speed is 150rpm, keeps temperature to be 30 DEG C, vibrate and after 12 hours, this matrix material is separated from solution, complete the process to divalence cadmium waste water.In solution, the concentration of remaining divalent cadmium ion uses atomic absorption spectrophotometry to measure, and the adsorptive capacity of calculating the results are shown in Table 1.
Table 1:pH value is on the impact of divalent cadmium ion in carboxylated magnetic oxygenated Graphene planar water
As known from Table 1, under too low pH value condition, carboxylated magnetic oxygenated Graphene is adsorbed with disadvantageous effect to cadmic, and along with the increase of pH, carboxylated magnetic oxygenated Graphene increases gradually to cadmic adsorptive capacity, and be just tending towards saturated when pH is 6, now adsorptive capacity is 147.89mg/g.
Embodiment 2:
One is of the present invention utilizes carboxylated magnetic oxygenated Graphene to remove cadmic method in waste water, comprises the following steps:
1. the preparation of carboxylated magnetic oxygenated Graphene
This step is identical with the step 1 of embodiment 1.
2. pair divalence cadmium waste water processes
The concentration of preparation 3 50mL is the divalence cadmium waste water of 10mg/L, is respectively 6 by nitric acid or sodium hydroxide adjust ph.The carboxylated magnetic oxygenated Graphene prepared by aforesaid method adds in above-mentioned 10 divalence cadmium waste waters, and the carboxylated magnetic oxygenated Graphene dry weight of adding in often liter of waste water counts 58mg.Reactor is placed in the vibration case that rotating speed is 150rpm, keeps temperature to be 30 DEG C, vibrate and after 12 hours, this matrix material is separated from solution, complete the process to divalence cadmium waste water.In solution, the concentration of remaining divalent cadmium ion uses atomic absorption spectrophotometry to measure, and the adsorptive capacity of calculating the results are shown in Table 2.
Table 2: temperature is on the impact of divalent cadmium ion in carboxylated magnetic oxygenated Graphene planar water
As shown in Table 2, the increase of temperature of reaction is favourable to divalent cadmium ion absorption, and when temperature of reaction is 15 DEG C, adsorptive capacity is 115.72mg/g, and when temperature of reaction is elevated to 45 DEG C, adsorptive capacity rises to 152.67mg/g.
Embodiment 3:
One is of the present invention utilizes carboxylated magnetic oxygenated Graphene to remove cadmic method in waste water, comprises the following steps:
1. the preparation of carboxylated magnetic oxygenated Graphene
This step is identical with the step 1 of embodiment 1.
2. pair divalence cadmium waste water processes
Above-mentioned obtained carboxylated magnetic oxygenated Graphene is added in the divalence cadmium waste water that initial pH value is 6, starting point concentration is 10mg/L, the carboxylated magnetic oxygenated Graphene dry weight of adding in often liter of waste water is 58mg, reactor is placed in the vibration case that rotating speed is 150rpm, temperature is kept to be 30 DEG C, within 5,10,20,40,60,120,240,360,540,720 minutes after starting of oscillation, sample respectively, use atomic absorption spectrophotometry to measure the concentration of remaining divalent cadmium ion in solution, the adsorptive capacity of calculating the results are shown in Table 3.
Table 3: carboxylated magnetic oxygenated Graphene in different time to the adsorption efficiency of divalent cadmium ion in water
As shown in Table 3, carboxylated magnetic oxygenated Graphene constantly increases along with continuing of duration of oscillation the adsorptive capacity of divalent cadmium ion, adsorbs and substantially reach stable after 60 minutes.
Below be only the preferred embodiment of the present invention, protection scope of the present invention be not only confined to above-described embodiment, conceives various process programs without substantial differences all in protection scope of the present invention with the present invention.
Claims (1)
1. one kind utilizes carboxylated magnetic oxygenated Graphene to remove cadmic method in waste water, said method comprising the steps of: get a certain amount of divalence cadmium waste water and adjust ph is 2.0 ~ 11.0, a certain amount of carboxylated magnetic oxygenated Graphene is added in waste water, the carboxylated magnetic oxygenated Graphene dry weight of adding in often liter of waste water is 0.02g ~ 5g, be react 0 ~ 24h in the constant temperature oscillator of 50rpm ~ 300rpm at rotating speed, and to control temperature of reaction be 10 DEG C ~ 50 DEG C, after having reacted, carboxylated magnetic oxygenated Graphene is separated from solution, complete removal cadmic in waste water,
Described carboxylated magnetic oxygenated Graphene is prepared by following steps:
(1) by 1.0 ~ 5.0g graphite, 1.0 ~ 5.0gK
2s
2o
8, 1.0 ~ 5.0gP
2o
5with 1 ~ 20mLH
2sO
4in heating in water bath to 60 ~ 100 DEG C after mixing, 0.2 ~ 1.0L ultrapure water is added after reaction 1 ~ 8h, 5 ~ 24h is placed after cooling, residual acid is removed with ultrapure water cleaning, 40 ~ 80 DEG C of vacuum-dryings, dried product to be added 80 ~ 150mL temperature be the mass concentration of 0 ~ 10 DEG C is the H of 95 ~ 98%
2sO
4in, then add 1.0 ~ 5.0gNaNO
3, 5 ~ 25gKMnO
4, and the 1 ~ 8h that vibrates at 0 ~ 20 DEG C, then at 20 ~ 50 DEG C of reaction 1 ~ 5h, then adds 0.1 ~ 0.5L water and ensures that temperature of reaction controls at 80 ~ 100 DEG C, continue vibration 2 ~ 10h, then adds 0.4 ~ 1.0L water and 10 ~ 40mL mass concentration is the H of 20 ~ 40%
2o
2, under room temperature vibrate 1 ~ 4h, then with mass concentration be 5 ~ 20% HCl and water repeatedly clean, then at 30 ~ 60 DEG C ultrasonic 1 ~ 3h, obtain the graphene oxide that concentration is 1 ~ 10g/L after constant volume;
(2) at room temperature, by the FeCl of 0.005 ~ 0.02mol
3with the FeSO of 0.002 ~ 0.01mol
4dissolve in 100 ~ 150mL ultrapure water, add in the graphene oxide solution described in 100 ~ 300mL step (1), add rapidly 10 ~ 100mL mass concentration be 30 ~ 90% ammoniacal liquor regulate pH be 9 ~ 11, and under 70 ~ 100 DEG C of conditions Keep agitation 10 ~ 60min, solution is made to be cooled to room temperature, extremely neutral with ultrapure water cleaning again, obtain the magnetic oxygenated Graphene that concentration is 1 ~ 10g/L after constant volume;
(3) at room temperature, by the magnetic oxygenated graphene solution of the 1 ~ 10mg/mL of 500 ~ 2000mL of step (2) gained, at room temperature 5 ~ 60min is stirred;
(4) volumetric concentration that the diethylene triamine pentacetic acid (DTPA) taking 1 ~ 10g is dissolved in 10 ~ 50mL is 1:1 ammoniacal liquor, adds in the magnetic oxygenated Graphene of step (3) gained, stirred at ambient temperature 5 ~ 30min after dissolving;
(5) add 5 ~ 50mL quadrol toward the solution of step (4) gained rapidly, use clean water after being heated to 50 ~ 100 DEG C of reaction 1 ~ 10h, constant volume obtains the carboxylated magnetic oxygenated Graphene that concentration is 1 ~ 10g/L.
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| CN106345466B (en) * | 2016-07-31 | 2020-05-01 | 江苏长三角环境科学技术研究院有限公司 | Preparation method of hydroxylated graphene oxide-magnesium titanate/silver molybdate composite material |
| CN107308913A (en) * | 2016-12-19 | 2017-11-03 | 华南农业大学 | A kind of magnetic oxygenated graphene of ethylenediamine graft modification and preparation method and application |
| CN107224961A (en) * | 2017-07-31 | 2017-10-03 | 陕西科技大学 | Carboxylated graphene oxide/ferriferrous oxide nano compound adsorbent for handling waste water containing chrome tanning and preparation method thereof |
| CN109569515A (en) * | 2018-12-25 | 2019-04-05 | 陕西省石油化工研究设计院 | A kind of preparation method of magnetic oxygenated graphene |
Citations (2)
| 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 |
| CN102989420A (en) * | 2012-12-11 | 2013-03-27 | 湖南大学 | Sulfonylation graphene oxide magnetic adsorbent, and preparation method and application thereof |
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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 |
| CN102989420A (en) * | 2012-12-11 | 2013-03-27 | 湖南大学 | Sulfonylation graphene oxide magnetic adsorbent, and preparation method and application thereof |
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