CN102806073A - Preparation method for cationic-type activated carbon - Google Patents
Preparation method for cationic-type activated carbon Download PDFInfo
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- CN102806073A CN102806073A CN2012103383251A CN201210338325A CN102806073A CN 102806073 A CN102806073 A CN 102806073A CN 2012103383251 A CN2012103383251 A CN 2012103383251A CN 201210338325 A CN201210338325 A CN 201210338325A CN 102806073 A CN102806073 A CN 102806073A
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Abstract
The invention relates to a preparation method for cationic-type activated carbon. The preparation method comprises the steps of washing, drying and crushing activated carbon, and oxidizing the activated carbon by concentrated hydrochloric acid or sulfuric acid so that the surface of the activated carbon has hydroxy; heating to the temperature of 80-87 DEG C under the condition of water bath, then adding epoxy chloropropane and N-N dimethylformamide, and stirring and reacting for 0.5-1.5h; and adding ethanediamine to react for 1-1.5h, then continuously dripping triethylamine to react for 0.5-1h, cooling to room temperature, and washing and drying so as to obtain the cationic-type activated carbon. An activated carbon product is the cationic-type activated carbon with positive charges, has a cationic group and a hydroxyl group, further has biodegradability, and is applicable to removing anionic-type pollutants in water.
Description
Technical field
The present invention relates to a kind of cationic preparation method of active carbon, be specifically related to a kind of organic matter such as ammonium salt that utilizes active carbon is carried out graft modification, prepare the positively charged preparation method of active carbon in surface, belong to preparation sorbing material technical field.
Background technology
Active carbon is a kind of sorbing material of wide spectrum, aspect water treatment, plays an important role.Along with progress of science and technology and development of industry and agriculture, problem of environmental pollution is serious day by day, and wherein water pollutes the most outstanding.To the complexity of pollutant in the water body, application is to having higher requirement to active carbon, and more and more researchers is devoted to prepare the active carbon of specific adsorption function.The characterization of adsorption of active carbon not only depends on its pore structure, but also relevant with its surface chemical property.Therefore activated carbon surface is carried out graft modification and handle, reach and better go out the purpose of the negative pollutant of anionic in the water body, be significant aspect the selectivity that improves active carbon.Do not find as yet up to now about preparing the public reported of cationic active carbon.
Summary of the invention
The present invention is directed to active carbon in the characteristics that have poor selectivity aspect the removal pollutant, a kind of cationic preparation method of active carbon is provided.The present invention utilizes the graft modification method to prepare positively charged cationic active carbon, and anionic pollutant is had electrostatic attraction ability preferably, is more suitable for the removal of anionic pollutant in to water body.
A kind of cationic preparation method of active carbon may further comprise the steps:
(1) Activated Carbon Pretreatment
With the active carbon washing, 80 ℃ ~ 100 ℃ dryings, be crushed to 100 ~ 200 orders, handle 8 ~ 10h with concentrated hydrochloric acid or sulfuric acid oxidation; The mass volume ratio of active carbon and concentrated hydrochloric acid or sulfuric acid is 2:8 ~ 10, the g/mL of unit; The mass concentration of said concentrated hydrochloric acid is 36 ~ 37%, and the mass concentration of sulfuric acid is 36 ~ 40%;
(2) the pretreated active carbon of step (1) is added reaction vessel, be warmed up to 80 ~ 87 ℃ under the water bath condition, add epoxychloropropane and N-N dimethyl formamide then, stirring reaction 0.5 ~ 1.5h; Said epoxychloropropane and N-N dimethyl formamide volume ratio are 1:1 ~ 1.2, and active carbon and epoxychloropropane mass volume ratio are 2:5 ~ 6, and unit is g/mL.
(3) drip ethylenediamine then, reaction 1 ~ 1.2h, said active carbon and ethylenediamine mass volume ratio are 2:3 ~ 4, unit is g/mL; Continue to drip triethylamine again, reaction 0.5 ~ 1h, said active carbon and triethylamine mass volume ratio are 2:4.5 ~ 5.5, unit is g/mL.
(4) reaction finishes to be cooled to room temperature, and washing is dry under 70 ~ 75 ℃, promptly gets cationic activated carbon product.
According to the present invention, preferred, in the said step (1), the use mass concentration is 36 ~ 36.5% hydrochloric acid Immesion active carbon, and oxidation processes 10h, the mass volume ratio of active carbon and said hydrochloric acid are 2g/10mL; Through this stage oxidation activated carbon surface, make activated carbon surface have more surface hydroxyl.
According to the present invention, preferred scheme is:
A kind of cationic preparation method of active carbon, step is following:
(1) Activated Carbon Pretreatment
With active carbon 2g washing, 80 ℃ of-100 ℃ of dryings, be crushed to the 100-200 order, with the hydrochloric acid 10mL oxidation processes 10h of mass concentration 36-36.5%;
(2) there-necked flask is put in the water-bath, be warmed up to 85 ℃, get the pretreated active carbon of step (1) and join wherein, add the 5ml epoxychloropropane then, 5mL N-N dimethyl formamide, stirring reaction 1h;
(3) continue to drip the 3mL ethylenediamine, reacted 1 hour; Continue Dropwise 5 mL triethylamine, reaction 30min;
(4) reaction finishes to be cooled to room temperature, and washing is dry under 70 ℃, promptly gets cationic activated carbon product.
The cationic activated carbon product that the present invention prepares is a kind of anion adsorbent, can be used for removing anionic pollutant in the water body.
Technical characterstic of the present invention and excellent results:
1, the active carbon after cleaning-drying is pulverized utilizes concentrated hydrochloric acid or sulfuric acid oxidation to handle, to increase the hydroxy functional group of activated carbon surface.
2, under catalyst action, adopt epoxychloropropane and amine substance etc. that active carbon is carried out chemical modification.In the chemical modification process, at first, hydroxyl that exists in the active carbon and epoxychloropropane generation nucleophilic substitution are connected to epoxy radicals on the active carbon and generate the outer ehter bond of the ring that contains epoxy radicals; Then, under the uniform temperature condition, amine substance (triethylamine and dimethylamine) makes the ternary epoxy ring-opening and introduces amine groups through nucleophilic addition with the aforesaid outer ehter bond of ring that contains epoxy radicals, forms the amine salt of positively charged.In above-mentioned course of reaction, epoxychloropropane plays the effect of a bridge formation, and amine substance is as grafting agent.
3, organic graft modification activated carbon surface cover tape ammonium salt on schedule utilizes this cationic active carbon to reach the effect of removing anionic pollutant in the water body.The present invention has overcome the characteristics of active carbon poor selectivity in the prior art; Make a kind of positively charged cationic active carbon; Products therefrom has cation group and oh group, and has biodegradability, is more suitable for the removal of anionic pollutant in to water body.
4, the cationic active carbon good stability of preparing can be realized the repeated multiple times utilization.
Description of drawings
Fig. 1 is the stereoscan photograph of the cationic active carbon that makes of embodiment 1.
Fig. 2 is the cationic active carbon that makes of embodiment 1 and the comparative sample raw material active carbon The adsorption kinetic data datagram to the anion potassium bichromate.
The specific embodiment
Below in conjunction with embodiment the present invention is further specified, but be not limited thereto.Concentration described in the embodiment is mass concentration.
Embodiment 1, a kind of positively charged cationic preparation method of active carbon may further comprise the steps:
(1) Activated Carbon Pretreatment: with active carbon 2g washing,, be crushed to the 100-200 order,, make its surface more hydroxyl occur with 36% hydrochloric acid 10mL oxidation processes active carbon 10h 80 ℃ of-100 ℃ of dryings;
(2) there-necked flask is put in the water-bath, be warmed up to 85 ℃, get the pretreated active carbon of step (1) and join wherein, add the 5mL epoxychloropropane then, 5mL N-N dimethyl formamide stirs 1h;
(3) add the 3mL ethylenediamine, this process reaction is violent, therefore slowly dropwise be incorporated as suitable.Reacted 1 hour; Continue again to add the 5mL triethylamine, reacted 30 minutes.
(4) reaction finishes to be cooled to room temperature, and washing is dry under 70 ℃, promptly gets cationic activated carbon product.
The sem photograph of the cationic active carbon that present embodiment makes is as shown in Figure 1: the adsorption dynamics adsorption kinetics data to the anion potassium bichromate are as shown in Figure 2.Dynamic experiment through contrast raw material active carbon and cationic adsorption agent of the present invention can know that the place to go effect of cationic active carbon centering chromate is significantly improved than raw material active carbon, and adsorption time also obviously shortens.
Embodiment 2,
Of embodiment 1, different is: handle active carbon 10h with 40% sulfuric acid oxidation during Activated Carbon Pretreatment, make its surface more hydroxyl occur.
Embodiment 3, a kind of cationic preparation method of active carbon may further comprise the steps:
(1) Activated Carbon Pretreatment
With active carbon 6g washing, 80 ℃ of-100 ℃ of dryings, be crushed to the 100-200 order, the concentrated hydrochloric acid 30mL dipping with 36.5% is handled 9h;
(2) get the pretreated active carbon of step (1) and add reaction vessel, be warmed up to 86 ℃ under the water bath condition, add epoxychloropropane 15mL and N-N dimethyl formamide 16mL then, stirring reaction 1.2h;
(3) drip ethylenediamine 10mL then, reaction 1.2h; Continue again to drip triethylamine 15mL, reacted 40 minutes.
(4) reaction finishes to be cooled to room temperature, and washing is dry under 70 ~ 75 ℃, promptly gets cationic activated carbon product.
Cationic active carbon is to the removal experiment of anionic pollutant in the water body
Experimental technique: adopt batch experiment; The cationic active carbon (anion adsorbent) that embodiment 1 is prepared is got in the conical flask of potassium bichromate solution that 0.1g is added to a series of 100mL of containing respectively at every turn; The concentration of anion potassium bichromate is 45mg/L, with the time timing sampling that adds behind the cationic active carbon, the concentration of dichromate ion is detected; Do three groups of parallel laboratory tests; Get its mean value, the experimental result that obtains is as shown in Figure 1, and Fig. 2 orbicular spot is represented the product group of embodiment 1.
Control group: at every turn get in the conical flask of potassium bichromate solution that raw material active carbon 0.1g is added to a series of 100mL of containing respectively; The concentration of anion dichromate ion is 45mg/L; Along with the time timing sampling, the concentration of dichromate ion is detected, do three groups of parallel laboratory tests; Get its mean value, the result who obtains is shown in side's point among Fig. 2;
Can find out from the check experiment result: the cationic active carbon of the present invention's preparation just reaches adsorption equilibrium in a short period of time as anion adsorbent; When reaching balance in the solution concentration of dichromate ion almost nil; Therefore; The place to go effect of cationic active carbon centering chromate is significantly improved than raw material active carbon, and adsorption time also obviously shortens.
Show further that through above test cationic active carbon of the present invention can effectively improve active carbon to anionic absorption removal effect in the water, the anion in the water body is had removal effect preferably, the important application prospect is arranged in water treatment.
Claims (3)
1. cationic preparation method of active carbon may further comprise the steps:
(1) Activated Carbon Pretreatment
With the active carbon washing, 80 ℃ ~ 100 ℃ dryings, be crushed to 100 ~ 200 orders, handle 8 ~ 10h with concentrated hydrochloric acid or sulfuric acid oxidation; The mass volume ratio of active carbon and concentrated hydrochloric acid or sulfuric acid is 2:8 ~ 10, the g/mL of unit; The mass concentration of said concentrated hydrochloric acid is 36 ~ 37%, and the mass concentration of sulfuric acid is 36 ~ 40%;
(2) the pretreated active carbon of step (1) is added reaction vessel, be warmed up to 80 ~ 87 ℃ under the water bath condition, add epoxychloropropane and N-N dimethyl formamide then, stirring reaction 0.5 ~ 1.5h; Said epoxychloropropane and N-N dimethyl formamide volume ratio are 1:1 ~ 1.2, and active carbon and epoxychloropropane mass volume ratio are 2:5 ~ 6, and unit is g/mL;
(3) drip ethylenediamine then, reaction 1 ~ 1.2h, said active carbon and ethylenediamine mass volume ratio are 2:3 ~ 4, unit is g/mL; Continue to drip triethylamine again, reaction 0.5 ~ 1h, said active carbon and triethylamine mass volume ratio are 2:4.5 ~ 5.5, unit is g/mL;
(4) reaction finishes to be cooled to room temperature, and washing is dry under 70 ~ 75 ℃, promptly gets cationic activated carbon product.
2. cationic preparation method of active carbon as claimed in claim 1 is characterized in that in the said step (1), and the use mass concentration is 36 ~ 36.5% hydrochloric acid Immesion active carbon, and oxidation processes 10h, the mass volume ratio of active carbon and said hydrochloric acid are 2g/10mL.
3. cationic preparation method of active carbon as claimed in claim 1 is characterized in that step is following:
(1) with active carbon 2g washing, 80 ℃ of-100 ℃ of dryings, is crushed to the 100-200 order, with the hydrochloric acid 10mL oxidation processes 10h of mass concentration 36-36.5%;
(2) there-necked flask is put in the water-bath, be warmed up to 85 ℃, get the pretreated active carbon of step (1) and join wherein, add the 5ml epoxychloropropane then, 5mL N-N dimethyl formamide, stirring reaction 1h;
(3) continue to drip the 3mL ethylenediamine, reacted 1 hour; Continue Dropwise 5 mL triethylamine, reaction 30min;
(4) reaction finishes to be cooled to room temperature, and washing is dry under 70 ℃, promptly gets cationic activated carbon product.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104014317A (en) * | 2014-06-19 | 2014-09-03 | 山东大学 | Preparation and application of modified magnetic straw anion adsorbent |
| CN104355311A (en) * | 2014-11-11 | 2015-02-18 | 山东大学 | Method capable of preparing active carbon by doping surfactant |
| CN104356285A (en) * | 2014-11-19 | 2015-02-18 | 辽宁大学 | Synthesis method of low-hardness high-crosslinking-degree PMMA (polymethyl methacrylate) microspheres |
| CN104941575A (en) * | 2014-03-25 | 2015-09-30 | 南京农业大学 | Multi-amino carbon composite material for selectively fixing mercury, chromium and lead in polluted soil and preparation method |
| 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 |
| CN106188925A (en) * | 2016-08-09 | 2016-12-07 | 叶剑 | A kind of polyphenylacetylene combination for clad plate and manufacture method thereof |
| CN108325503A (en) * | 2018-02-22 | 2018-07-27 | 北京师范大学 | A kind of amido-activated carbon composite drug of removal anionic pollutant |
| CN108686620A (en) * | 2018-05-04 | 2018-10-23 | 同济大学 | A kind of modifying method of activated carbon that can be effectively increased channel surfaces positive charge radical amount |
| CN109179838A (en) * | 2018-10-11 | 2019-01-11 | 凯莱英生命科学技术(天津)有限公司 | The processing method of DMF waste water containing triethylamine |
| 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 |
| CN110142030A (en) * | 2019-04-02 | 2019-08-20 | 广东宏庭环保科技有限公司 | A kind of preparation method of the efficient formaldehyde adsorbent material based on active carbon |
| CN113210023A (en) * | 2021-04-29 | 2021-08-06 | 黄山学院 | Biochar-based anion exchanger and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020011447A1 (en) * | 1999-09-30 | 2002-01-31 | Waldmann John J. | Chemical composition for treatment of nitrate and odors from water streams and process wastewater treatment |
| WO2002100509A1 (en) * | 2001-06-08 | 2002-12-19 | The Penn State Research Foundation | A method for perchlorate removal from ground water |
| CN101318125A (en) * | 2008-07-04 | 2008-12-10 | 山东大学 | Method for preparing poly-epoxychloropropane dimethylamine cation alta-mud |
-
2012
- 2012-09-13 CN CN201210338325.1A patent/CN102806073B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020011447A1 (en) * | 1999-09-30 | 2002-01-31 | Waldmann John J. | Chemical composition for treatment of nitrate and odors from water streams and process wastewater treatment |
| WO2002100509A1 (en) * | 2001-06-08 | 2002-12-19 | The Penn State Research Foundation | A method for perchlorate removal from ground water |
| CN101318125A (en) * | 2008-07-04 | 2008-12-10 | 山东大学 | Method for preparing poly-epoxychloropropane dimethylamine cation alta-mud |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941575A (en) * | 2014-03-25 | 2015-09-30 | 南京农业大学 | Multi-amino carbon composite material for selectively fixing mercury, chromium and lead in polluted soil and preparation method |
| CN104014317B (en) * | 2014-06-19 | 2016-02-03 | 山东大学 | A kind of preparation and application of modified magnetic stalk anion adsorbent |
| CN104014317A (en) * | 2014-06-19 | 2014-09-03 | 山东大学 | Preparation and application of modified magnetic straw anion adsorbent |
| CN104355311A (en) * | 2014-11-11 | 2015-02-18 | 山东大学 | Method capable of preparing active carbon by doping surfactant |
| CN104356285A (en) * | 2014-11-19 | 2015-02-18 | 辽宁大学 | Synthesis method of low-hardness high-crosslinking-degree PMMA (polymethyl methacrylate) microspheres |
| 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 |
| CN106188925A (en) * | 2016-08-09 | 2016-12-07 | 叶剑 | A kind of polyphenylacetylene combination for clad plate and manufacture method thereof |
| 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 |
| CN108325503A (en) * | 2018-02-22 | 2018-07-27 | 北京师范大学 | A kind of amido-activated carbon composite drug of removal anionic pollutant |
| CN108686620A (en) * | 2018-05-04 | 2018-10-23 | 同济大学 | A kind of modifying method of activated carbon that can be effectively increased channel surfaces positive charge radical amount |
| CN108686620B (en) * | 2018-05-04 | 2020-11-10 | 同济大学 | Active carbon modification method capable of effectively increasing number of positive charge groups on surface of pore channel |
| CN109179838A (en) * | 2018-10-11 | 2019-01-11 | 凯莱英生命科学技术(天津)有限公司 | The processing method of DMF waste water containing triethylamine |
| CN110142030A (en) * | 2019-04-02 | 2019-08-20 | 广东宏庭环保科技有限公司 | A kind of preparation method of the efficient formaldehyde adsorbent material based on active carbon |
| CN110142030B (en) * | 2019-04-02 | 2021-10-29 | 山西龙清环保新材料有限公司 | Preparation method of efficient formaldehyde adsorption material based on activated carbon |
| CN113210023A (en) * | 2021-04-29 | 2021-08-06 | 黄山学院 | Biochar-based anion exchanger and preparation method and application thereof |
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