CN104045123A - Method for removing divalent cadmium in wastewater by using carboxylated magnetic graphene oxide - Google Patents
Method for removing divalent cadmium in wastewater by using carboxylated magnetic graphene oxide Download PDFInfo
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- CN104045123A CN104045123A CN201410327625.9A CN201410327625A CN104045123A CN 104045123 A CN104045123 A CN 104045123A CN 201410327625 A CN201410327625 A CN 201410327625A CN 104045123 A CN104045123 A CN 104045123A
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- magnetic oxygenated
- oxygenated graphene
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Abstract
The invention discloses a method for removing divalent cadmium in wastewater by using carboxylated magnetic graphene oxide. The method comprises the following steps of taking a certain quantity of divalent cadmium wastewater, and regulating the pH value of the divalent cadmium wastewater to 2.0-11.0 (preferably 5.0-7.0, most preferably 6); adding a certain quantity of carboxylated magnetic graphene oxide into the wastewater, wherein the dry weight of carboxylated magnetic graphene oxide added in every liter of wastewater is 0.02-5g; reacting in a constant-temperature oscillator with the rotating speed of 50-300rpm for 0-24h (most preferably 1-6h) while controlling the reaction temperature at 10-50 DEG C (most preferably 20-40 DEG C); separating carboxylated magnetic graphene oxide from the solution after the reaction is ended to finish the removal of divalent cadmium in wastewater. The method has the advantages of low cost, convenience in operation, high treatment efficiency, easiness for separation and recovery and the like.
Description
Technical field
The invention belongs to environment functional material and water treatment new technical field, relate in particular to a kind of carboxylated magnetic oxygenated Graphene in the application of processing in 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 is more and more, and the environment such as soil, water body that the mankind depend on for existence has been subjected to serious heavy metal contamination, and is aggravation trend.When heavy metal content has exceeded certain limit, can cause the deterioration of the ecological environment and quality of agricultural product to decline, finally have a strong impact on the mankind's health.Cadmium is as a heavy metal species, can respiratory tract be produced and be stimulated, long-term exposure can cause anosmia, gum macula lutea or gradually become yellow circle, cadmic compound is difficult for by intestinal absorption, but can in breathing body, absorb, 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 expense is higher, and regeneration exists 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, limited the widespread use of these sorbent materials.Therefore, preparing a kind of sorbent material that can address these problems is of great immediate significance.
Graphene oxide is the product of powdered graphite through chemical oxidation and after peeling off, and is single atomic shell, in oxidising process, makes many oxy radicals such as C-O-C, C-OH, and C=O, COOH etc. are connected with graphite linings covalency.These functional groups can be used as adsorption site and metal ion produces sequestering action, but due to its wetting ability, are difficult to afterwards separate from waste water in absorption.Solve this problem by magnetic nano-particle being loaded on to the magnetic oxygenated Graphene synthesizing on graphene oxide surface, but the puzzlement bringing is in magnetic history, some adsorption sites on graphene oxide surface are occupied by magnetic nano-particle, cause magnetic oxygenated Graphene adsorption site to reduce, adsorptive power has also reduced.In order to improve its adsorptive power, just need to increase adsorption site heavy metal ion to stronger sequestering action on its surface.A lot of amino and carboxyl are carried in diethylenetriamine tetraacethyl surface, can produce good envelope effect, but it are as sorbent treatment heavy metal, is not easy to realize solid-liquid separation to heavy metal and organic pollutant.Diethylene triamine pentacetic acid (DTPA) is formed to matrix material by certain method grafting to magnetic oxygenated Graphene surface, increased the adsorption site of magnetic oxygenated Graphene, improved its adsorptive power to heavy metal ion, and easily realized solid-liquid separation.Also carboxylated magnetic oxygenated Graphene is not applied at present to the precedent of cadmium wastewater processing.
Summary of the invention
Technical problem to be solved by this invention is: the deficiency existing for prior art, provides that a kind of operational condition is simple, easy to implement, applied range, cost is low, efficiency the is high carboxylated magnetic oxygenated Graphene that utilizes 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: getting a certain amount of divalence cadmium waste water and regulating pH value is 2.0～11.0 (to be 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 every liter of waste water is 0.02g～5g, in the constant temperature oscillator that is 50rpm～300rpm at rotating speed, react 0～24h (most preferably being 1h～6h), 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 cadmic removal in waste water.
In technique scheme, described carboxylated magnetic oxygenated Graphene makes by following steps:
(1) by 1.0～5.0g graphite, 1.0～5.0g K
2s
2o
8, 1.0～5.0g P
2o
5with 1～20mL H
2sO
4after mixing in heating in water bath to 60～100 DEG C, after reaction 1～8h, add 0.2～1.0L ultrapure water, cooling rear placement 5～24h, cleans and removes residual acid with ultrapure water, 40～80 DEG C of vacuum-dryings, it is the H of 0～10 DEG C that dried product is added to 80～150mL temperature
2sO
4in (95～98%), then add 1.0～5.0g NaNO
3, 5～25g KMnO
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 to ensure that temperature of reaction is controlled at 80～100 DEG C, continue vibration 2～10h, then add 0.4～1.0L water and 10～40mL H
2o
2(20～40wt%), the 1～4h that vibrates under room temperature, then use HCl (5～20%) and water repeatedly to clean, then at 30～60 DEG C ultrasonic 1～3h, after constant volume, obtain the graphene oxide that concentration is 1～10g/L;
(2) at room temperature, by the FeCl of 0.005～0.02mol
3feSO with 0.002～0.01mol
4incorporate in 100～150mL ultrapure water, add in the described graphene oxide solution of 100～300mL step (1), adding rapidly 10～100mL ammoniacal liquor (massfraction is 30～90%) to regulate pH is 9～11, and under 70～100 DEG C of conditions continue stir 10～60min, make solution be cooled to room temperature, clean to neutral with ultrapure water, after constant volume, obtaining concentration is the magnetic oxygenated Graphene of 1～10g/L again;
(3) at room temperature,, by the magnetic oxygenated graphene solution of 1～10mg/mL of 500～2000mL of step (2) gained, at room temperature stir 5～60min;
(4) volumetric concentration that the diethylene triamine pentacetic acid (DTPA) that takes 1～10g is dissolved in 10～50mL is 1:1 ammoniacal liquor, adds in the magnetic oxygenated Graphene of step (3) gained after dissolving, under room temperature, stirs 5～30min;
(5) rapidly add 5～50mL quadrol toward the solution of step (4) gained, be heated to clean with clear water after 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 is preferably controlled at 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 using 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 carries out absorption reaction, after having reacted, utilize magnet to realize solid-liquid separation.Whole treatment process cost is lower, and operation more simply and is easily implemented, and is easy to, from solution after treatment, carboxylated magnetic oxygenated Graphene is separated to recycling;
3. method of the present invention can effectively be processed divalence cadmium waste water, and the improvement of polluting for heavy metal in waste water provides new approach.
Embodiment
Below with reference to specific embodiment, the present invention is described in further details.
Embodiment 1:
A kind of cadmic method in carboxylated magnetic oxygenated Graphene removal waste water of utilizing of the present invention, comprises the following steps:
1. the preparation of carboxylated magnetic oxygenated Graphene
(1) by 3.0g graphite, 2.5g K
2s
2o
8, 2.5g P
2o
5with 1～20mL H
2sO
4after mixing, in heating in water bath to 60～100 DEG C, reaction adds 0.5L ultrapure water after 4h, and cooling rear placements 12h cleans the residual acid of removal with ultrapure water, and 60 DEG C of vacuum-dryings, it is the H of 0 DEG C that dried product is added to 120mL temperature
2sO
4(98%) in, then add 2.5g NaNO
3, 15g KMnO
4, and the 4h that vibrates at 20 DEG C, then at 35 DEG C of reaction 2h, then add 250mL water to ensure that temperature of reaction is controlled at 90 DEG C, continue vibration 1h, then add 0.5L water and 20mL H
2o
2(30%), the 2h that vibrates under room temperature, then use HCl (mass concentration is 10%) and water repeatedly to clean, then at 50 DEG C ultrasonic 2h, after constant volume, obtain the graphene oxide that concentration is 5.2g/L;
(2) at room temperature, by the FeCl of 0.01mol
3feSO with 0.005mol
4incorporate in 120mL ultrapure water, add in the described graphene oxide solution of 200mL step (1), adding rapidly proper ammonia to regulate pH is 10, and under 85 DEG C of conditions continue stir 45min, make solution be cooled to room temperature, clean to neutral with ultrapure water, after constant volume, obtaining concentration is the magnetic oxygenated Graphene of 4.6g/L again;
(3) at room temperature,, by the magnetic oxygenated graphene solution of 1～10g/L of the 1200mL of step (2) gained, at room temperature stir 5～60min;
(4) volumetric concentration that the diethylene triamine pentacetic acid (DTPA) that takes 3.0g is dissolved in 20mL is 1:1 ammoniacal liquor, adds in the magnetic oxygenated Graphene of step (3) gained after dissolving, under room temperature, stirs 10min;
(5) rapidly add 18mL quadrol toward the solution of step (4) gained, be heated to clean with clear water after 80 DEG C of reaction 6h, after constant volume, obtaining concentration is the carboxylated magnetic oxygenated Graphene of 2.9g/L.
2. pair divalence cadmium waste water is processed
Configure 10 divalence cadmium waste waters that 50mL concentration is 10mg/L, regulate pH value to be respectively 2,3,4,5,6,7,8,9,10,11 with nitric acid or sodium hydroxide.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 every liter of waste water is counted 58mg.Reactor is placed in to the vibration case that rotating speed is 150rpm, and keeping temperature is 30 DEG C, vibrates and after 12 hours, this matrix material is separated from solution, completes the processing to divalence cadmium waste water.In solution, the concentration of remaining divalent cadmium ion is used atomic absorption spectrophotometry to measure, and the adsorptive capacity of calculating the results are shown in Table 1.
The impact of table 1:pH value on 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 has disadvantageous effect to cadmic absorption, and along with the increase of pH, carboxylated magnetic oxygenated Graphene increases gradually to cadmic adsorptive capacity, and be to be just tending towards saturated at 6 o'clock at pH, now adsorptive capacity is 147.89mg/g.
Embodiment 2:
A kind of cadmic method in carboxylated magnetic oxygenated Graphene removal waste water of utilizing of the present invention, 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 is processed
The concentration of 3 50mL of the preparation divalence cadmium waste water that is 10mg/L, regulates pH value to be respectively 6 with nitric acid or sodium hydroxide.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 every liter of waste water is counted 58mg.Reactor is placed in to the vibration case that rotating speed is 150rpm, and keeping temperature is 30 DEG C, vibrates and after 12 hours, this matrix material is separated from solution, completes the processing to divalence cadmium waste water.In solution, the concentration of remaining divalent cadmium ion is used atomic absorption spectrophotometry to measure, and the adsorptive capacity of calculating the results are shown in Table 2.
Table 2: the impact of temperature on 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 in the time that temperature of reaction is elevated to 45 DEG C, adsorptive capacity rises to 152.67mg/g.
Embodiment 3:
A kind of cadmic method in carboxylated magnetic oxygenated Graphene removal waste water of utilizing of the present invention, 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 is processed
The above-mentioned carboxylated magnetic oxygenated Graphene making 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 every liter of waste water is 58mg, reactor is placed in to the vibration case that rotating speed is 150rpm, keeping temperature is 30 DEG C, sampling respectively in 5,10,20,40,60,120,240,360,540,720 minutes after starting of oscillation, 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 adsorption efficiency to divalent cadmium ion in water in different time
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, and after 60 minutes, absorption reaches stable substantially.
Below be only the preferred embodiment of the present invention, protection scope of the present invention is also 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 (5)
1. one kind is utilized carboxylated magnetic oxygenated Graphene to remove cadmic method in waste water, said method comprising the steps of: getting a certain amount of divalence cadmium waste water and regulating pH value is 2.0～11.0 (to be 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 every liter of waste water is 0.02g～5g, in the constant temperature oscillator that is 50rpm～300rpm at rotating speed, react 0～24h (most preferably being 1h～6h), 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 cadmic removal in waste water.
2. according to claim 1ly utilize carboxylated magnetic oxygenated Graphene to remove cadmic method in waste water, it is characterized in that, described carboxylated magnetic oxygenated Graphene is to prepare by following steps:
(1) by 1.0～5.0g graphite, 1.0～5.0g K
2s
2o
8, 1.0～5.0g P
2o
5with 1～20mL H
2sO
4after mixing in heating in water bath to 60～100 DEG C, after reaction 1～8h, add 0.2～1.0L ultrapure water, cooling rear placement 5～24h, cleans and removes residual acid with ultrapure water, 40～80 DEG C of vacuum-dryings, it is the H of 0～10 DEG C that dried product is added to 80～150mL temperature
2sO
4in (95～98%), then add 1.0～5.0g NaNO
3, 5～25g KMnO
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 to ensure that temperature of reaction is controlled at 80～100 DEG C, continue vibration 2～10h, then add 0.4～1.0L water and 10～40mL H
2o
2(20～40wt%), the 1～4h that vibrates under room temperature, then use HCl (5～20%) and water repeatedly to clean, then at 30～60 DEG C ultrasonic 1～3h, after constant volume, obtain the graphene oxide that concentration is 1～10g/L;
(2) at room temperature, by the FeCl of 0.005～0.02mol
3feSO with 0.002～0.01mol
4incorporate in 100～150mL ultrapure water, add in the described graphene oxide solution of 100～300mL step (1), adding rapidly 10～100mL ammoniacal liquor (massfraction is 30～90%) to regulate pH is 9～11, and under 70～100 DEG C of conditions continue stir 10～60min, make solution be cooled to room temperature, clean to neutral with ultrapure water, after constant volume, obtaining concentration is the magnetic oxygenated Graphene of 1～10g/L again;
(3) at room temperature,, by the magnetic oxygenated graphene solution of 1～10mg/mL of 500～2000mL of step (2) gained, at room temperature stir 5～60min;
(4) volumetric concentration that the diethylene triamine pentacetic acid (DTPA) that takes 1～10g is dissolved in 10～50mL is 1:1 ammoniacal liquor, adds in the magnetic oxygenated Graphene of step (3) gained after dissolving, under room temperature, stirs 5～30min;
(5) rapidly add 5～50mL quadrol toward the solution of step (4) gained, be heated to clean with clear water after 50～100 DEG C of reaction 1～10h, constant volume obtains the carboxylated magnetic oxygenated Graphene that concentration is 1～10g/L.
3. according to claim 1ly utilize carboxylated magnetic oxygenated Graphene to remove cadmic method in waste water, it is characterized in that: the wastewater pH before described absorption reaction is controlled at 5.0～7.0.
4. according to claim 1ly utilize carboxylated magnetic oxygenated Graphene to remove cadmic method in waste water, it is characterized in that: described absorption reaction temperature is controlled at 10～50 DEG C.
5. according to claim 1ly utilize carboxylated magnetic oxygenated Graphene to remove cadmic method in waste water, it is characterized in that: in described waste water, the concentration of cadmium is controlled at 5mg/L～300mg/L.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106345466A (en) * | 2016-07-31 | 2017-01-25 | 上田环境修复股份有限公司 | Method for preparing hydroxylation graphene oxide-magnesium titanate/silver molybdate composite materials |
| 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 |
| 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 |
| 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)
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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 |
| CN102989420A (en) * | 2012-12-11 | 2013-03-27 | 湖南大学 | Sulfonylation graphene oxide magnetic adsorbent, and preparation method and application thereof |
-
2014
- 2014-07-10 CN CN201410327625.9A patent/CN104045123B/en not_active Expired - Fee Related
Patent 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106345466A (en) * | 2016-07-31 | 2017-01-25 | 上田环境修复股份有限公司 | Method for preparing hydroxylation graphene oxide-magnesium titanate/silver molybdate composite materials |
| 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 |
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