CN102806073B - Preparation method for cationic-type activated carbon - Google Patents
Preparation method for cationic-type activated carbon Download PDFInfo
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- CN102806073B CN102806073B CN201210338325.1A CN201210338325A CN102806073B CN 102806073 B CN102806073 B CN 102806073B CN 201210338325 A CN201210338325 A CN 201210338325A CN 102806073 B CN102806073 B CN 102806073B
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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 preparation method of cationic active carbon, be specifically related to one and utilize the organic matters such as ammonium salt to carry out graft modification to active carbon, prepare the preparation method of the active carbon of surface band positive charge, belong to and prepare sorbing material technical field.
Background technology
Active carbon is a kind of sorbing material of wide spectrum, plays an important role in water treatment.Along with the progress of science and technology and the development of industrial or agricultural, problem of environmental pollution is day by day serious, and wherein water pollutions is the most outstanding.For the complexity of pollutant in water body, application is had higher requirement to active carbon, and increasing researcher is devoted to the active carbon preparing 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 graft modification process is carried out to activated carbon surface, reaches and better go out anionic in water body and bear the object of pollutant, improve active carbon selective in be significant.Not yet find the open report about the cationic active carbon of preparation up to now.
Summary of the invention
The present invention is directed to active carbon removing the feature that there is poor selectivity in pollutant, a kind of preparation method of cationic active carbon is provided.The present invention utilizes graft modification method to prepare positively charged cationic active carbon, has good electrostatic attraction ability to anionic pollutant, is more suitable for the removal to anionic pollutant in water body.
A preparation method for cationic active carbon, comprises the following steps:
(1) Activated Carbon Pretreatment
Active carbon is washed, dry, pulverize to 100 ~ 200 orders at 80 DEG C ~ 100 DEG C, with concentrated hydrochloric acid or sulfuric acid oxidation process 8 ~ 10h; The mass volume ratio of active carbon and concentrated hydrochloric acid or sulfuric acid is 2:8 ~ 10, unit g/mL; The mass concentration of described concentrated hydrochloric acid is 36 ~ 37%, and the mass concentration of sulfuric acid is 36 ~ 40%;
(2) step (1) pretreated active carbon is added reaction vessel, under water bath condition, be warmed up to 80 ~ 87 DEG C, then add epoxychloropropane and N-N dimethyl formamide, stirring reaction 0.5 ~ 1.5h; Described 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) then drip ethylenediamine, reaction 1 ~ 1.2h, described active carbon and ethylenediamine mass volume ratio are 2:3 ~ 4, and unit is g/mL; Continue to drip triethylamine, reaction 0.5 ~ 1h, described active carbon and triethylamine mass volume ratio are 2:4.5 ~ 5.5, and unit is g/mL again.
(4) react end and be cooled to room temperature, washing, dry at 70 ~ 75 DEG C, obtain cationic activated carbon product.
According to the present invention, preferably, in described step (1), be the hydrochloric acid Immesion active carbon of 36 ~ 36.5% by mass concentration, oxidation processes 10h, the mass volume ratio of active carbon and described hydrochloric acid is 2g/10mL; By this stage oxidation activated carbon surface, make activated carbon surface with more surface hydroxyl.
According to the present invention, preferred scheme is:
A preparation method for cationic active carbon, step is as follows:
(1) Activated Carbon Pretreatment
Active carbon 2g is washed, dry, pulverize to 100-200 order at 80 DEG C-100 DEG C, with the hydrochloric acid 10mL oxidation processes 10h of mass concentration 36-36.5%;
(2) there-necked flask is put in water-bath, be warmed up to 85 DEG C, get step (1) pretreated active carbon and join wherein, then add 5ml epoxychloropropane, 5mL N-N dimethyl formamide, stirring reaction 1h;
(3) continue to drip 3mL ethylenediamine, react 1 hour; Continue to drip 5mL triethylamine, reaction 30min;
(4) react end and be cooled to room temperature, washing, dry at 70 DEG C, obtain 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 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 process, to increase the hydroxy functional group of activated carbon surface.
2, under catalyst action, epoxychloropropane and amine substance etc. is adopted to carry out chemical modification to active carbon.In chemical modification process, first, the hydroxyl existed in active carbon and epoxychloropropane generation nucleophilic substitution, be connected to epoxy radicals on active carbon and generate the outer ehter bond of the ring containing epoxy radicals; Then, under uniform temperature condition, amine substance (triethylamine and dimethylamine) makes ternary epoxy ring-opening by nucleophilic addition with the outer ehter bond of the aforesaid ring containing epoxy radicals and introduces amine groups, forms the amine salt of positively charged.In above-mentioned course of reaction, epoxychloropropane plays an effect of building bridge, 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 removing anionic pollutant in water body.Instant invention overcomes the feature of active carbon poor selectivity in prior art, obtained 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 to anionic pollutant in water body.
4, the cationic active carbon good stability prepared, can realize repeated multiple times utilization.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the cationic active carbon that embodiment 1 obtains.
Fig. 2 is that the obtained cationic active carbon of embodiment 1 and comparative sample raw material active carbon are to the adsorption kinetic data datagram of anion potassium bichromate.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, but be not limited thereto.Concentration described in embodiment is mass concentration.
The preparation method of embodiment 1, a kind of positively charged cationic active carbon, comprises the following steps:
(1) Activated Carbon Pretreatment: washed by active carbon 2g, dry, pulverize to 100-200 order at 80 DEG C-100 DEG C, with 36% hydrochloric acid 10mL oxidation processes active carbon 10h, makes its surface occur more hydroxyl;
(2) there-necked flask is put in water-bath, be warmed up to 85 DEG C, get step (1) pretreated active carbon and join wherein, then add 5mL epoxychloropropane, 5mL N-N dimethyl formamide, stir 1h;
(3) add 3mL ethylenediamine, this process reaction is violent, therefore slowly dropwise be incorporated as suitable.React 1 hour; Continue again to add 5mL triethylamine, react 30 minutes.
(4) react end and be cooled to room temperature, washing, dry at 70 DEG C, obtain cationic activated carbon product.
The scanning electron microscope (SEM) photograph of the cationic active carbon that the present embodiment obtains is as shown in Figure 1: to the adsorption dynamics adsorption kinetics data of anion potassium bichromate as shown in Figure 2.Known by the dynamic experiment of contrast raw material active carbon and subject cationic type adsorbent, 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,
As described in Example 1, difference is: with 40% sulfuric acid oxidation process active carbon 10h during Activated Carbon Pretreatment, makes its surface occur more hydroxyl.
The preparation method of embodiment 3, a kind of cationic active carbon, comprises the following steps:
(1) Activated Carbon Pretreatment
Washed by active carbon 6g, dry, pulverize to 100-200 order at 80 DEG C-100 DEG C, the concentrated hydrochloric acid 30mL with 36.5% floods, process 9h;
(2) get step (1) pretreated active carbon and add reaction vessel, under water bath condition, be warmed up to 86 DEG C, then add epoxychloropropane 15mL and N-N dimethyl formamide 16mL, stirring reaction 1.2h;
(3) then ethylenediamine 10mL is dripped, reaction 1.2h; Continue again to drip triethylamine 15mL, react 40 minutes.
(4) react end and be cooled to room temperature, washing, dry at 70 ~ 75 DEG C, obtain cationic activated carbon product.
Cationic active carbon is tested the removal of anionic pollutant in water body
Experimental technique: adopt a batch experiment, the cationic active carbon (anion adsorbent) embodiment 1 prepared is got 0.1g at every turn and is added in the conical flask of a series of potassium bichromate solution containing 100mL respectively, the concentration of anion potassium bichromate is 45mg/L, with adding the time timing sampling after cationic active carbon, the concentration of dichromate ion is detected, do three groups of parallel laboratory tests, get its mean value, as shown in Figure 1, Fig. 2 orbicular spot represents the product group of embodiment 1 to the experimental result obtained.
Control group: get raw material active carbon 0.1g at every turn and be added in the conical flask of a series of potassium bichromate solution containing 100mL respectively, the concentration of anion dichromate ion is 45mg/L, along with time timing sampling, the concentration of dichromate ion is detected, do three groups of parallel laboratory tests, get its mean value, the result obtained is as shown in side's point in Fig. 2;
As can be seen from check experiment result: cationic active carbon prepared by the present invention just reaches adsorption equilibrium in a short period of time as anion adsorbent, when reaching balance, in solution, the concentration of dichromate ion is 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 that cationic active carbon of the present invention effectively can improve the Adsorption effect of active carbon to anion in water further by above test, to the anion in water body, there is good removal effect, in water treatment, have important application prospect.
Claims (1)
1., for removing a preparation method for the cationic active carbon of anionic pollutant in water body, step is as follows:
(1) Activated Carbon Pretreatment: washed by active carbon 2g, dry, pulverize to 100-200 order at 80 DEG C-100 DEG C, with the hydrochloric acid 10mL oxidation processes 10h of mass concentration 36%;
(2) there-necked flask is put in water-bath, be warmed up to 85 DEG C, get step (1) pretreated active carbon and join wherein, then add 5mL epoxychloropropane, 5mL N-N dimethyl formamide, stirring reaction 1h;
(3) continue to drip 3mL ethylenediamine, this process reaction is violent, therefore slowly dropwise be incorporated as suitable, react 1 hour; Continue again to drip 5mL triethylamine, reaction 30min;
(4) react end and be cooled to room temperature, washing, dry at 70 DEG C, obtain cationic activated carbon product;
In described water body, anionic pollutant is potassium bichromate.
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| 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 |
| CN104355311A (en) * | 2014-11-11 | 2015-02-18 | 山东大学 | Method capable of preparing active carbon by doping surfactant |
| CN104356285B (en) * | 2014-11-19 | 2017-02-22 | 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 |
| 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 |
| CN108325503B (en) * | 2018-02-22 | 2021-03-16 | 北京师范大学 | Amino-activated carbon composite medicament for removing anionic pollutants |
| 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 |
| 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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