CN105056884A - Preparation method for activated carbon material for drinking water purification - Google Patents
Preparation method for activated carbon material for drinking water purification Download PDFInfo
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- CN105056884A CN105056884A CN201510434719.0A CN201510434719A CN105056884A CN 105056884 A CN105056884 A CN 105056884A CN 201510434719 A CN201510434719 A CN 201510434719A CN 105056884 A CN105056884 A CN 105056884A
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Abstract
The present invention discloses a preparation method for an activated carbon material for drinking water purification. By virtue of an adsorption improver, cryogenic freezing treatment and supercritical water treatment, pore size distribution of the activated carbon is improved. Compared to the prior art, according to a catalytic material provided by the invention, by taking modified activated carbon as a carrier, the number and proportion of mesopores in the activated carbon are increased, the adsorption capacity of small molecule organic substances is stronger, and meanwhile few macropores exist in the pore size distribution, so that the activated carbon material has a certain adsorption capacity on bacteria and microorganisms. Moreover, the adsorbent has the characteristic of being good in formability, can be processed to various specific shapes, and is convenient to mount and use.
Description
Technical field
The present invention relates to active carbon adsorption material of a kind of energy deepling purification of drinking water and preparation method thereof, belong to technical field of water purification.
Background technology
Increasingly sharpen along with at water pollutions, content of organics in urban drinking water source significantly improves, and most domestic waterworks still adopts conventional water-purifying process, the clearance of 40% can only be reached to the organic pollution of the low concentration in water source, be difficult to ensure the safe and reliable of drinking water, therefore the further treatment technique of drinking water is paid close attention to widely.
Absorbent charcoal material is a kind of important amorphous carbon cellulosic material, is black porosu solid, stable chemical nature, pore structure is flourishing, and having huge specific area, is a kind of excellent adsorbent, there is abundant pore passage structure and huge specific area, be widely used in every field.The wide material sources of active carbon, can utilize any material such as timber, sawdust, coal, shell, bone etc. containing carbon to prepare as raw material.Because active carbon has special microstructure, hole is flourishing, has extremely strong adsorption function, regenerating easily and wide material sources, and therefore active carbon is widely used in the advanced treating of drinking water in recent years.
Charcoal absorption process water technology be the sixties in last century from external introduction, its application and development lifts huge progress in recent years.The major pollutants nitrobenzene of water pollution in Songhuajiang River accident in 2005, conventional water technology clearance is used only to have 2-5%, but nitrobenzene is easily by charcoal treatment, in emergency processing, takes the method for being adsorbed by active carbon powder and activated carbon granule co-treatment, achieve successfully.
But because the size distribution of active carbon mainly concentrates on micropore district, and micropore size for organic macromolecule and microorganism is less than normal, be difficult to play suction-operated, therefore usually need activated carbon powder to be broken into very little particle and use or activated carbon granule is bonded together use.Although Powdered Activated Carbon adsorption effect is fine, is difficult to process, is inconvenient to use; Use that binding agent is easy again causes secondary pollution to water quality.Therefore change the pore-size distribution of active carbon, improving its performance is current study hotspot.
CN104761018A discloses the method utilizing active carbon to carry out water treatment, comprises the steps: in water treatment technology, select active carbon to carry out water treatment; Described active carbon is according to following Standard Selection: select iodine sorption value to be greater than 950mg/g and the adsorptive value of methylene blue is greater than the active carbon of 200mg/g; Or select aperture to be not less than the active carbon of the organic molecule diameter 1.7 times in water treatment.
CN103752269A discloses a kind of modified activated carbon and preparation method thereof.This modified activated carbon has very high adsorption capacity to Cr (VI) ion in water body, has adsorption capacity high simultaneously, has good treatment effect to the heavy metal-containing polluted water of high concentration.The active carbon of this invention is by the multi-step chemical modification to original activity charcoal, makes the functional group that activated carbon surface is graft-functionalized, thus significantly improves the adsorption capacity of active carbon for Cr.
CN101125691A discloses a kind of method utilizing active carbon fibre peacekeeping ozone oxidization combination to carry out water treatment.Arrange the NACF of single or multiple lift through modification at reactor bottom, in reactor, NACF consumption is 1-50g/L, and concentration of ozone gas is 5-12mg/L, and the processing time is 5-90min.Active carbon is placed in retort carry out re-activation to the modification of NACF, activation process is except steam, one or both in carbon dioxide, ammonia and metallic salt can also be selected as activator, improve ratio activated carbon surface being greater than the aperture of 0.7-2.5nm.
Summary of the invention
The object of the present invention is to provide acticarbon of a kind of separating formaldehyde from air and preparation method thereof, at room temperature adsorbent provided by the invention effectively can absorb the formaldehyde in air, and adsorption capacity is large, long service life.
For a preparation method for the absorbent charcoal material of drink water purifying, comprise the following steps:
1) aqueous solution that mass concentration is the soluble nitrate of 10-20% is prepared; 2) active carbon is immersed in step 1) 10-24h in the aqueous solution that obtains; 3) active carbon freezing 1-24h under the low temperature of-30 DEG C to-10 DEG C of the aqueous solution will be impregnated of; 4) 120-150 DEG C of dry 1-3h is warming up to; 5) under condition of supercritical water, 1-3h is activated; 6) after washing is washed with hydrogen peroxide under normal temperature; 7) drying obtains modified active high-area carbon; Described soluble nitrate is one or more in sodium nitrate, potassium nitrate, calcium nitrate, and preferred soluble nitrate is calcium nitrate.
The middle hole number of described modified active high-area carbon accounts for more than 30% of total duct quantity.
Described absorbent charcoal carrier comes from plant or coal processing obtains, and preferred described absorbent charcoal carrier comes from calcined anthracite preparation, and the burn tinctuer in preparation process is 25-40%, and preferred burn tinctuer is 25-30%; More preferably the preparation of active carbon comprises the following steps: anthracite removing impurity is also ground into the particle that particle diameter is 0.01-0.1mm; Adding polymethacrylates stirs shaping, calcines 10-24h, at 800-900 DEG C, calcine 5-12h at 100-150 DEG C, activates 1-24h, namely obtain described absorbent charcoal carrier under 750-800 DEG C and water vapor conditions.
The present invention also provides a kind of modified activated carbon utilizing described method to prepare, and utilizes described modified activated carbon process water, the especially method of drinking water.
In general, in water see the molecular diameter of organic pollution all at 1-50nm, namely belong to the scope of the mesopore (diameter 2-50nm) in hole division, and its distribution of pores of common active carbon is substantially all in the scope of micropore (diameter is less than 2nm), therefore common charcoal treatment Organic substance in water and the effect of bacterium are also bad.The present invention, by improving the processing of active carbon, significantly adds the quantity of mesopore hole in active carbon, and containing a small amount of macropore hole, improves the adsorption effect of active carbon to harmful substances such as Organic substance in water molecule and virus and bacterias.Absorbent charcoal carrier disclosed by the invention is improved one's methods not to be needed to add extra loaded article, avoids the secondary pollution to water body.Certainly, absorbent charcoal carrier disclosed by the invention also can as carrier material, and absorption in advance has the material of specific function, to reaching better effect.
The present invention adopts freezing process active carbon, utilize water generation volumetric expansion after freezing to be dissolved in the nitrate part crystallize out in water simultaneously, partial pore duct is caved in, makes borehole enlargement, form larger mesopore duct, form macropore duct even on a small quantity; Nitrate crystal part in the process of drying of crystallization is simultaneously retained in duct, under condition of supercritical water subsequently, physicochemical reaction occurs, further improves the pore passage structure of active carbon.In the modification of this external active carbon, add appropriate calcium and also contribute to increasing hole number in active carbon.
Compared with prior art, catalysis material of the present invention is using the active carbon of modification as carrier, add the middle hole number in active carbon and ratio, the ability of absorption small molecule organic compound is stronger, also have a small amount of macropore to exist simultaneously in pore-size distribution, also have certain adsorption capacity to bacterium and microorganism.In addition this adsorbent also has the feature of good moldability, also can be processed into various given shape, easy to install and use.
Detailed description of the invention
The present invention is further illustrated below by embodiment
Embodiment 1
Anthracite removing impurity is also ground into the particle that particle diameter is 0.01-0.1mm; Adding polymethacrylates stirs shaping, calcines 10h, at 800 DEG C, calcine 12h at 120 DEG C, activates 24h, namely obtain active carbon under 800 DEG C and water vapor conditions; Preparation mass concentration is the aqueous solution of the calcium nitrate of 20%; Active carbon is immersed in 10h in the aqueous solution obtained; Active carbon freezing 5h under the low temperature of-30 DEG C of the aqueous solution will be impregnated of; Be warming up to 120 DEG C of dry 3h; 3h is activated under condition of supercritical water; After washing is washed with hydrogen peroxide under normal temperature; Drying obtains modified active high-area carbon;
Embodiment 2
Burn tinctuer is adopted to be the active carbon from coal of 30%; Calcium nitrate and sodium nitrate are the aqueous solution of 25% according to the proportions mass concentration of 3: 1, and active carbon is immersed in 10h in the aqueous solution obtained; Active carbon freezing 10h under the low temperature of-20 DEG C of the aqueous solution will be impregnated of; Be warming up to 150 DEG C of dry 2h; 3h is activated under condition of supercritical water; After washing is washed with hydrogen peroxide under normal temperature; Drying obtains modified active high-area carbon;
Comparative example 1
Without the normal activated carbon of modification
Comparative example 2
Through the active carbon of supercritical water treatment
Carry out water treatmenting performance evaluation contrast to the active carbon of modified activated carbon disclosed by the invention and other method process, adopt the aqueous solution of the 100ppm concentration of different material to carry out Static Adsorption 1h, result is as shown in the table
| Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | |
| Heavy metal | 98.2 | 96.5 | 63.0 | 82.7 |
| Benzoic acid | 99.1 | 98.9 | 45.9 | 63.8 |
| COD | 96.3 | 91.5 | 40.6 | 55.8 |
As can be seen from adsorption test data, adsorbent of the present invention is comprehensive absorption property better, especially has good adsorption effect to organic impurities.
Claims (7)
1., for a preparation method for the absorbent charcoal material of drink water purifying, comprise the following steps:
1) aqueous solution that mass concentration is the soluble nitrate of 10-20% is prepared; 2) active carbon is immersed in step 1) 10-24h in the aqueous solution that obtains; 3) active carbon freezing 1-24h under the low temperature of-30 DEG C to-10 DEG C of the aqueous solution will be impregnated of; 4) 120-150 DEG C of dry 1-3h is warming up to; 5) under condition of supercritical water, 1-3h is activated; 6) after washing is washed with hydrogen peroxide under normal temperature; 7) drying obtains modified active high-area carbon; Described soluble nitrate is one or more in sodium nitrate, potassium nitrate, calcium nitrate, and preferred soluble nitrate is calcium nitrate.
2. the preparation method of a kind of absorbent charcoal material for drink water purifying according to claim 1, is characterized in that the middle hole number of described modified active high-area carbon accounts for more than 30% of total duct quantity.
3. the preparation method of a kind of absorbent charcoal material for drink water purifying according to claim 1, is characterized in that described absorbent charcoal carrier comes from plant or coal processing obtains.
4. the preparation method of a kind of absorbent charcoal material for drink water purifying according to claim 1, is characterized in that described absorbent charcoal carrier comes from anthracite, and the burn tinctuer in calcining preparation process is 25-40%, and preferred burn tinctuer is 25-30%.
5. the preparation method of a kind of absorbent charcoal material for drink water purifying according to claim 5, the preparation coming from anthracitic absorbent charcoal carrier described in it is characterized in that comprises the following steps: anthracite removing impurity is also ground into the particle that particle diameter is 0.01-0.1mm; Adding polymethacrylates stirs shaping, calcines 10-24h, at 800-900 DEG C, calcine 5-12h at 100-150 DEG C, activates 1-24h, namely obtain described absorbent charcoal carrier under 750-800 DEG C and water vapor conditions.
6. the modified activated carbon utilizing the method as described in claim 1-5 to prepare.
7. the method utilizing modified activated carbon as claimed in claim 6 to carry out water treatment.
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Cited By (6)
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| CN106277287A (en) * | 2016-08-31 | 2017-01-04 | 江苏兴海环保科技有限公司 | A kind of preparation method for cultivating microorganism carrier |
| CN106277361A (en) * | 2016-08-31 | 2017-01-04 | 江苏兴海环保科技有限公司 | A kind of preparation method for water treatment carrier of giving up |
| CN110092433A (en) * | 2019-04-24 | 2019-08-06 | 湖南大学 | A method of it is leaked based on regulation activity charcoal medium with reducing pathogenic bacteria in drinking water |
| CN110240233A (en) * | 2019-06-18 | 2019-09-17 | 江苏居安环保设备有限公司 | A kind of preparation method and applications of modification bamboo charcoal |
| CN111389366A (en) * | 2020-04-20 | 2020-07-10 | 南华大学 | Modification method of activated carbon, modified activated carbon and application thereof |
| CN113244885A (en) * | 2021-04-25 | 2021-08-13 | 龙岩市华研活性炭科技有限公司 | Modified activated carbon for aquarium filtration and adsorption and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106277287A (en) * | 2016-08-31 | 2017-01-04 | 江苏兴海环保科技有限公司 | A kind of preparation method for cultivating microorganism carrier |
| CN106277361A (en) * | 2016-08-31 | 2017-01-04 | 江苏兴海环保科技有限公司 | A kind of preparation method for water treatment carrier of giving up |
| CN110092433A (en) * | 2019-04-24 | 2019-08-06 | 湖南大学 | A method of it is leaked based on regulation activity charcoal medium with reducing pathogenic bacteria in drinking water |
| CN110240233A (en) * | 2019-06-18 | 2019-09-17 | 江苏居安环保设备有限公司 | A kind of preparation method and applications of modification bamboo charcoal |
| CN110240233B (en) * | 2019-06-18 | 2022-04-22 | 江苏居安环境工程有限公司 | Preparation method and application of modified bamboo charcoal |
| CN111389366A (en) * | 2020-04-20 | 2020-07-10 | 南华大学 | Modification method of activated carbon, modified activated carbon and application thereof |
| CN111389366B (en) * | 2020-04-20 | 2022-04-26 | 南华大学 | Modification method of activated carbon, modified activated carbon and application thereof |
| CN113244885A (en) * | 2021-04-25 | 2021-08-13 | 龙岩市华研活性炭科技有限公司 | Modified activated carbon for aquarium filtration and adsorption and preparation method thereof |
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Effective date of registration: 20170831 Address after: 226600 Nantong City, Haian Province, Haian Town, Pingqiao village, Group No. three, No. 10, No. Applicant after: Cao Xiaojuan Address before: 226600 No. 208 Jianghai West Road, Haian County, Jiangsu, Nantong Applicant before: NANTONG MINGWU E-COMMERCE CO., LTD. |
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Effective date of registration: 20180522 Address after: 511517 one of Chuangxing two road 10, high tech Industrial Development Zone, Qingyuan, Guangdong. Applicant after: Qingyuan Huaxin drink Co., Ltd. Address before: 226600 No. 10, group three, Pingqiao village, Haian Town, Haian, Nantong, Jiangsu. Applicant before: Cao Xiaojuan |
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