CN103752269A - Modified active carbon and preparation method thereof - Google Patents
Modified active carbon and preparation method thereof Download PDFInfo
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- CN103752269A CN103752269A CN201410032772.3A CN201410032772A CN103752269A CN 103752269 A CN103752269 A CN 103752269A CN 201410032772 A CN201410032772 A CN 201410032772A CN 103752269 A CN103752269 A CN 103752269A
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Abstract
The invention discloses a modified active carbon, and a preparation method of the modified active carbon. The modified active carbon has high absorptive efficiency and high absorptive capacity on Cr(VI) ions in water, and good treatment effect on high-concentration heavy metal polluted water. Moreover, the raw active carbon is subjected to multi-step chemical modification by the preparation method, so that the surface of the active carbon is grafted with functional groups, so that the absorptive capacity of the active carbon on the Cr(VI) ions in water is greatly improved. The preparation method has other features of easily available raw material, low cost, and suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of modified activated carbon, also relate to the preparation method of this modified activated carbon, belong to adsorbent field.
Background technology
In recent years, along with various industrial wastes enter water body, the content of Heavy Metals in Waters is more and more higher, and the water that contains heavy metal ion stops and is accumulated in environment due to long-term, by food chain enrichment step by step, will have a strong impact on the safety of the mankind and other biological.In addition, heavy metal acute poisoning can make that people vomits, weak, stupor and even dead, and chronic sympton is to make people's immunity low for a long time, and various tumours, chronic disease are multiple.Wherein Cr (VI) is common heavy metal pollution of water body thing, is prevalent in plating, process hides and dyeing waste water, has stronger carcinogenicity.
Although at present there is abundant pore structure, high specific area and enough chemical stabilities for removing the active carbon of Heavy Metals in Waters ion, but common charcoal absorption capacity is low, especially not good to the heavy metal-polluted water treatment effect of high concentration, and its adsorption saturation time is long.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of modified activated carbon Cr in water body (VI) ion to high absorption capacity.
The technical problem that the present invention also will solve is to provide above-mentioned preparation method Cr in water body (VI) ion to the modified activated carbon of high absorption capacity.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is:
A kind of modified activated carbon, its chemical structural formula is:
。
The preparation method of above-mentioned modified activated carbon: first use hydrochloric acid purifying active carbon, remove the impurity of activated carbon surface, by the active carbon after purifying through nitric acid oxidation processing, active carbon after oxidation is at N, under N-dicyclohexylcarbodiimide (DCC) effect, with ethylenediamine generation graft reaction, active carbon after ethylenediamine modification is reacted with vanillic aldehyde, finally the active carbon after vanillic aldehyde modification is obtained to modified activated carbon of the present invention by sodium borohydride reduction, preparation method of the present invention specifically comprises the steps:
Step 1, carries out purifying and oxidation processes successively by a certain amount of active carbon, and by washing active carbon after treatment, oven dry;
Step 2, the active carbon that step 1 is obtained adds in ethylenediamine, and active carbon and ethylenediamine generation graft reaction under the effect of dehydrating condensation agent, by reacted product washing, oven dry;
Step 4, the product that step 3 is obtained reacts with sodium borohydride, and reacted product washing, oven dry can be obtained to required modified activated carbon.
Wherein, in step 1, the scarvenger that described purification process adopts is hydrochloric acid, and the volumetric concentration of described hydrochloric acid is 10%, and the purifying time is 10～14 hours.
Wherein, in step 1, the oxidant that described oxidation processes adopts is nitric acid, and the concentration of described nitric acid is 5mol/L, and the temperature of described oxidation processes is 50 ℃, and oxidization time is 6h.
Wherein, in step 1, the product pH>5 after washing, bake out temperature is 50 ℃.
Wherein, in step 2, often add 1g active carbon, the volume of required ethylenediamine is 20～25ml, and the mass ratio of active carbon and dehydrating condensation agent is 1:0.5～1:1, and wherein, the temperature of graft reaction is 100～115 ℃, and the reaction time is 12h.
Wherein, in step 3, the active carbon after graft reaction and the mass ratio of vanillic aldehyde are 1:0.5～1:1.5, and wherein, described reaction temperature is 50～75 ℃, and the reaction time is 12h.
Wherein, in step 4, the active carbon after vanillic aldehyde modification and the mass ratio of sodium borohydride are 1:0.5～1:1.5, and wherein, described reaction temperature is 20～30 ℃, and the reaction time is 24h.
Wherein, in step 1, described active carbon is 40～80 orders.
Wherein, in step 2, described dehydrating condensation agent is N, N-dicyclohexylcarbodiimide.
The preparation principle of modified activated carbon of the present invention: the present invention is take active carbon (AC) as raw material, through hydrochloric acid purifying, remove activated carbon surface impurity, again the active carbon after purifying is obtained after nitric acid treatment to the active carbon (AC-COOH) of contain-COOH of surface, at N, under the effect of N-dicyclohexylcarbodiimide, in the active carbon of contain-COOH of surface and ethylenediamine molecule-NH
2there is dehydration, obtain AC-EDA, the active carbon after ethylenediamine modification with in vanillic aldehyde molecule-CHO reacts, and obtains AC=Van, finally AC=Van, again through sodium borohydride reduction, obtains final modified activated carbon AC-Van.
Beneficial effect: than prior art, modified activated carbon of the present invention has high adsorption capacity to Cr in water body (VI) ion, its adsorption capacity is high simultaneously, and the heavy metal-containing polluted water of high concentration is had to good treatment effect; In addition, preparation method of the present invention is by the multistep chemical modification to original activity charcoal, the functional group of functionalization that made activated carbon surface grafting, thereby increased substantially the adsorption capacity of active carbon to Cr in water body (VI) ion, preparation method's raw material of the present invention is easy to get, cost is low, be suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is modified activated carbon preparation method's of the present invention process chart;
Fig. 2 is the absorption property figure of modified activated carbon of the present invention and original activity charcoal;
Fig. 3 is the kinetic curve figure of modified activated carbon of the present invention;
Fig. 4 is the Changing Pattern figure of modified activated carbon absorption property of the present invention with pH value;
Fig. 5 is the adsorption isotherm schematic diagram of original activity charcoal;
Fig. 6 is the adsorption isotherm schematic diagram of modified activated carbon of the present invention.
The specific embodiment
Below in conjunction with drawings and Examples, technical scheme of the present invention is elaborated.
Embodiment 1
A preparation method for modified activated carbon, comprises the steps:
Step 1, it is purifying 12h in 10% hydrochloric acid that a certain amount of raw material active carbon (AC) is joined to volumetric concentration, and the washing active carbon after purifying is dried to neutrality at 110 ℃; Nitric acid oxidation processes 6h at 50 ℃ by the active carbon after 4g purifying through 5mol/L, then washs the active carbon after oxidation to pH>5 and at 50 ℃ and dries by deionized water, obtains AC-COOH;
Step 2, getting the active carbon that 2g step 1 obtains adds in 45mL ethylenediamine, in solution, add again 1gN, N-dicyclohexylcarbodiimide (DCC) constantly stirs, 12h refluxes at 100 ℃, active carbon and ethylenediamine generation graft reaction, to neutral and product is dried at 80 ℃, obtain AC-EDA with the product after ethanol and deionized water washing reaction;
Step 4, gets the product that 1g step 3 obtains and in absolute ethyl alcohol, reacts 24h with 1g sodium borohydride, and reaction temperature is 25 ℃, by deionized water and acetone washing for reacted product, and dries at 60 ℃, can obtain modified activated carbon AC-Van of the present invention.
Embodiment 2
A preparation method for modified activated carbon, comprises the steps:
Step 1, it is purifying 14h in 10% hydrochloric acid that a certain amount of raw material active carbon (AC) is joined to volumetric concentration, and the washing active carbon after purifying is dried to neutrality at 110 ℃; The nitric acid that is 5mol/L through concentration by the active carbon after 4g purifying is oxidation processes 6h at 50 ℃, then the active carbon after oxidation is washed to pH>5 and at 50 ℃ and is dried by deionized water, obtains AC-COOH;
Step 2, getting the active carbon that 2g step 1 obtains adds in 45mL ethylenediamine, in solution, add again 1.5gN, N-dicyclohexylcarbodiimide (DCC) constantly stirs, 12h refluxes at 105 ℃, active carbon and ethylenediamine generation graft reaction, to neutral and product is dried at 80 ℃, obtain AC-EDA with the product after ethanol and deionized water washing reaction;
Step 4, gets the product that 1g step 3 obtains and in absolute ethyl alcohol, reacts 24h with 1g sodium borohydride, and reaction temperature is 25 ℃, by deionized water and acetone washing for reacted product, and dries at 60 ℃, can obtain modified activated carbon AC-Van of the present invention.
A preparation method for modified activated carbon, comprises the steps:
Step 1, it is purifying 12h in 10% hydrochloric acid that a certain amount of raw material active carbon (AC) is joined to volumetric concentration, and the washing active carbon after purifying is dried to neutrality at 110 ℃; The nitric acid that is 5mol/L through concentration by the active carbon after 4g purifying is oxidation processes 6h at 50 ℃, then the active carbon after oxidation is washed to pH>5 and at 50 ℃ and is dried by deionized water, obtains AC-COOH;
Step 2, getting the active carbon that 2g step 1 obtains adds in 45mL ethylenediamine, in solution, add again 1.5gN, N-dicyclohexylcarbodiimide (DCC) constantly stirs, 12h refluxes at 115 ℃, active carbon and ethylenediamine generation graft reaction, to neutral and product is dried at 80 ℃, obtain AC-EDA with the product after ethanol and deionized water washing reaction;
Step 4, gets the product that 1g step 3 obtains and in absolute ethyl alcohol, reacts 24h with 1g sodium borohydride, and reaction temperature is 25 ℃, by deionized water and acetone washing for reacted product, and dries at 60 ℃, can obtain modified activated carbon AC-Van of the present invention.
Embodiment 4
A preparation method for modified activated carbon, comprises the steps:
Step 1, it is purifying 10h in 10% hydrochloric acid that a certain amount of raw material active carbon (AC) is joined to volumetric concentration, and the washing active carbon after purifying is dried to neutrality at 110 ℃; The nitric acid that is 5mol/L through concentration by the active carbon after 4g purifying is oxidation processes 6h at 50 ℃, then the active carbon after oxidation is washed to pH>5 and at 50 ℃ and is dried by deionized water, obtains AC-COOH;
Step 2, getting the active carbon that 2g step 1 obtains adds in 45mL ethylenediamine, in solution, add again 1.5gN, N-dicyclohexylcarbodiimide (DCC) constantly stirs, 12h refluxes at 110 ℃, active carbon and ethylenediamine generation graft reaction, to neutral and product is dried at 80 ℃, obtain AC-EDA with the product after ethanol and deionized water washing reaction;
Step 4, gets the product that 1g step 3 obtains and in absolute ethyl alcohol, reacts 24h with 1.5g sodium borohydride, and reaction temperature is 30 ℃, by deionized water and acetone washing for reacted product, and dries at 60 ℃, can obtain modified activated carbon AC-Van of the present invention.
Comparative example:
Measure respectively AC-Van and the adsorption capacity of original activity charcoal to Cr in solution (VI) ion of embodiment 1～4 preparation:
Get the solution that 50mL Cr (VI) concentration is 40mg/L, the AC-Van adsorbent that adds 0.05g embodiment 1 to prepare, constant temperature oscillation 1.5h, upon adsorption reaching after balance, take out solution, and after centrifugal with supercentrifuge, measure the concentration of Cr (VI) ion in supernatant, according to following formula
(1) obtain adsorbance, in (1) formula: Q is adsorbance (mg/g), C
0for adsorbing the concentration (mg/L) of Cr in front solution (VI), C
efor adsorbing the concentration (mg/L) of Cr in rear solution (VI), V is liquor capacity (L), and W is adsorbent mass (g); Result as shown in Figure 2;
Get the solution that 50mL Cr (VI) concentration is 40mg/L, the AC-Van adsorbent that adds 0.05g embodiment 2 to prepare, constant temperature oscillation 1.5h, upon adsorption reaching after balance, take out solution, and after centrifugal with supercentrifuge, measure the concentration of Cr (VI) ion in supernatant, obtain adsorbance, result as shown in Figure 2;
Get the solution that 50mL Cr (VI) concentration is 40mg/L, the AC-Van adsorbent that adds 0.05g embodiment 3 to prepare, constant temperature oscillation 1.5h, upon adsorption reaching after balance, take out solution, and after centrifugal with supercentrifuge, measure the concentration of Cr (VI) ion in supernatant, obtain adsorbance, result as shown in Figure 2;
Get the solution that 50mL Cr (VI) concentration is 40mg/L, the AC-Van adsorbent that adds 0.05g embodiment 4 to prepare, constant temperature oscillation 1.5h, upon adsorption reaching after balance, take out solution, and after centrifugal with supercentrifuge, measure the concentration of Cr (VI) ion in supernatant, obtain adsorbance, result as shown in Figure 2;
Get the solution that 50mL Cr (VI) concentration is 40mg/L, add 0.05g original activity carbon adsorbent, constant temperature oscillation 1.5h, upon adsorption reaching after balance, take out solution, and after centrifugal with supercentrifuge, measure the concentration of Cr (VI) ion in supernatant, obtain adsorbance, result as shown in Figure 2.
Utilize the Cr (VI) in AC-Van adsorbent solution prepared by embodiment 3:
(1) adsorption dynamics adsorption kinetics
Get the solution that 200mL Cr (VI) concentration is 40mg/L and be placed in tool plug conical flask, the AC-Van adsorbent that adds 0.2g embodiment 3 to prepare, constant temperature in constant temperature oscillator (25 ℃) vibration, after interval certain hour takes out solution and uses supercentrifuge centrifugal, measure the concentration of Cr (VI) in supernatant, according to following formula
obtain adsorbance Q
t, and draw the relation curve of adsorbance-time, result as shown in Figure 3, wherein, in above formula: Q
tfor adsorbance (mg/g), C
0for adsorbing the concentration (mg/L) of Cr in front solution (VI), C
efor adsorbing the concentration (mg/L) in rear solution, V is liquor capacity (L), and W is adsorbent mass (g).
(2) impact of pH value
Get solution that a series of 50mL Cr (VI) concentration is 40mg/L in tool plug conical flask, the AC-Van adsorbent that adds respectively 0.05g embodiment 3 to prepare, under condition of different pH, constant temperature oscillation 1.5h, upon adsorption reaching after balance, take out solution, and after centrifugal with supercentrifuge, measure the concentration of Cr (VI) in supernatant, obtain adsorbance, and draw out the relation curve of adsorbance and pH value, see Fig. 4, as shown in Figure 4, in pH=1～3 o'clock, the adsorbance of AC-Van adsorbent is higher, when pH>3, the adsorbance of AC-Van adsorbent increases with pH and declines rapidly, therefore the active carbon of modification is pH=1～3 to the optimal adsorption pH scope of Cr in water body (VI).
(3) adsorption isotherm model
Get the different solution of a series of 50mL Cr (VI) concentration, all add 0.05g original activity charcoal, constant temperature oscillation 1.5h, upon adsorption reaching after balance, takes out solution, and after centrifugal with supercentrifuge, measure the concentration of Cr (VI) in supernatant, obtain adsorbance, and draw the relation curve of adsorbance-equilibrium concentration, see Fig. 5;
Get the different solution of a series of 50mL Cr (VI) concentration, the AC-Van that all adds 0.05g embodiment 3 to prepare, constant temperature oscillation 1.5h, upon adsorption reaching after balance, takes out solution, and after centrifugal with supercentrifuge, measure the concentration of Cr (VI) in supernatant, obtain adsorbance, and draw the relation curve of adsorbance-equilibrium concentration, see Fig. 6.
Obviously, above-described embodiment is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also giving exhaustive to all embodiments.And these belong to apparent variation that spirit of the present invention extended out or variation still among protection scope of the present invention.
Claims (10)
1. a modified activated carbon, is characterized in that: its chemical structural formula is:
2. a preparation method for modified activated carbon described in claim 1, is characterized in that: comprise the steps:
Step 1, carries out purifying and oxidation processes successively by a certain amount of active carbon, and by washing active carbon after treatment, oven dry;
Step 2, the active carbon that step 1 is obtained adds in ethylenediamine, and active carbon and ethylenediamine generation graft reaction under the effect of dehydrating condensation agent, by reacted product washing, oven dry;
Step 3, reacts the product of step 2 gained with vanillic aldehyde, by reacted product washing, oven dry;
Step 4, the product that step 3 is obtained reacts with sodium borohydride, and reacted product washing, oven dry can be obtained to required modified activated carbon.
3. the preparation method of modified activated carbon according to claim 2, is characterized in that: in step 1, the scarvenger that described purification process adopts is hydrochloric acid, and the volumetric concentration of described hydrochloric acid is 10%, and the purifying time is 10～14 hours.
4. the preparation method of modified activated carbon according to claim 2, is characterized in that: in step 1, the oxidant that described oxidation processes adopts is nitric acid, and the concentration of described nitric acid is 5mol/L, and the temperature of described oxidation processes is 50 ℃, and oxidization time is 6h.
5. the preparation method of modified activated carbon according to claim 2, is characterized in that: in step 1, and the product pH>5 after washing, bake out temperature is 50 ℃.
6. the preparation method of modified activated carbon according to claim 2, it is characterized in that: in step 2, often add 1g active carbon, the volume of required ethylenediamine is 20～25ml, the mass ratio of active carbon and dehydrating condensation agent is 1:0.5～1:1, wherein, the temperature of graft reaction is 100～115 ℃, and the reaction time is 12h.
7. the preparation method of modified activated carbon according to claim 2, is characterized in that: in step 3, the active carbon after graft reaction and the mass ratio of vanillic aldehyde are 1:0.5～1:1.5, wherein, described reaction temperature is 50～75 ℃, and the reaction time is 12h.
8. the preparation method of modified activated carbon according to claim 2, is characterized in that: in step 4, the active carbon after vanillic aldehyde modification and the mass ratio of sodium borohydride are 1:0.5～1:1.5, wherein, described reaction temperature is 20～30 ℃, and the reaction time is 24h.
9. the preparation method of modified activated carbon according to claim 2, is characterized in that: in step 1, described active carbon is 40～80 orders.
10. the preparation method of modified activated carbon according to claim 2, is characterized in that: in step 2, described dehydrating condensation agent is N, N-dicyclohexylcarbodiimide.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103949220A (en) * | 2014-05-14 | 2014-07-30 | 河海大学 | Modified activated carbon and preparation method thereof |
| CN105056884A (en) * | 2015-07-23 | 2015-11-18 | 南通名物电子商务有限公司 | Preparation method for activated carbon material for drinking water purification |
| CN105921108A (en) * | 2016-05-28 | 2016-09-07 | 中国科学院新疆理化技术研究所 | Preparation method and application of montmorillonoid and carbon composite material |
| CN105984869A (en) * | 2015-01-30 | 2016-10-05 | 克州生产力促进中心(有限公司) | Method for preparing ethylenediamine modified activated carbon |
| CN108726593A (en) * | 2018-05-22 | 2018-11-02 | 临泉县盈昌农副产品有限公司 | A kind of production technology for the clear ginger wastewater purificant being based primarily upon COD and SS |
| CN109422381A (en) * | 2017-08-31 | 2019-03-05 | 宝山钢铁股份有限公司 | A kind for the treatment of process removing cold rolling reverse osmosis concentrated water dissolved organic carbon and total chromium |
| CN110368899A (en) * | 2019-07-16 | 2019-10-25 | 邱越 | A kind of absorbent charcoal composite material and its preparation method and application |
| CN110368898A (en) * | 2019-07-16 | 2019-10-25 | 邱越 | A kind of absorbent charcoal composite material and preparation method thereof for sewage treatment |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103949220A (en) * | 2014-05-14 | 2014-07-30 | 河海大学 | Modified activated carbon and preparation method thereof |
| CN103949220B (en) * | 2014-05-14 | 2015-11-18 | 河海大学 | A kind of modified activated carbon and preparation method thereof |
| CN105984869A (en) * | 2015-01-30 | 2016-10-05 | 克州生产力促进中心(有限公司) | Method for preparing ethylenediamine modified activated carbon |
| CN105056884A (en) * | 2015-07-23 | 2015-11-18 | 南通名物电子商务有限公司 | Preparation method for activated carbon material for drinking water purification |
| CN105056884B (en) * | 2015-07-23 | 2018-06-26 | 清远华新达饮品有限公司 | A kind of preparation method of absorbent charcoal material for drink water purifying |
| CN105921108A (en) * | 2016-05-28 | 2016-09-07 | 中国科学院新疆理化技术研究所 | Preparation method and application of montmorillonoid and carbon composite material |
| CN109422381A (en) * | 2017-08-31 | 2019-03-05 | 宝山钢铁股份有限公司 | A kind for the treatment of process removing cold rolling reverse osmosis concentrated water dissolved organic carbon and total chromium |
| CN109422381B (en) * | 2017-08-31 | 2022-06-24 | 宝山钢铁股份有限公司 | Treatment process for removing soluble organic carbon and total chromium in cold rolling reverse osmosis concentrated water |
| CN108726593A (en) * | 2018-05-22 | 2018-11-02 | 临泉县盈昌农副产品有限公司 | A kind of production technology for the clear ginger wastewater purificant being based primarily upon COD and SS |
| CN110368899A (en) * | 2019-07-16 | 2019-10-25 | 邱越 | A kind of absorbent charcoal composite material and its preparation method and application |
| CN110368898A (en) * | 2019-07-16 | 2019-10-25 | 邱越 | A kind of absorbent charcoal composite material and preparation method thereof for sewage treatment |
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