CN101774576B - Modified active carbon , preparation method and application thereof - Google Patents
Modified active carbon , preparation method and application thereof Download PDFInfo
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- CN101774576B CN101774576B CN 201010101049 CN201010101049A CN101774576B CN 101774576 B CN101774576 B CN 101774576B CN 201010101049 CN201010101049 CN 201010101049 CN 201010101049 A CN201010101049 A CN 201010101049A CN 101774576 B CN101774576 B CN 101774576B
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Abstract
The invention provides a modified active carbon and a preparation method application thereof. The method comprises the following steps of: placing active carbon into a quartz pipe of a muffle furnace; filling nitrogen in the muffle furnace at room temperature for 1-2 hours, wherein the gas flow rate is 80-120ml/min; then heating the muffle furnace to 400-800 DEG C at the speed of 10 DEG C/min under the protection of the same nitrogen flow and maintaining for 1-4 hours; after the temperature is reduced to 25 DEG C, stopping filling the nitrogen; continuously filling air at the flow rate of 80-120ml/min for 1hour and taking out to obtain the modified active carbon. The modified active carbon is used as an adsorbent and used for removing organic pollutants in the process of water treatment, has the advantages of high purifying ability and long service life and particularly can solve the problem of poor maneuverability on high-concentration phenol endocrine distributing object polluted water by the traditional water treatment method.
Description
(1) technical field
What the present invention relates to is a kind of modified activated carbon, the present invention also relates to a kind of preparation method of active carbon, the invention still further relates to modified activated carbon as sorbent material, the application method in the water treatment of removing the phenols incretion obscurant.
(2) background technology
Got into since 21st century; Quickening along with the Chinese society development process; China's pollution of waterhead situation is also more severe; The water source, various places all receives pollution in various degree, and the generation of particularly various sudden pollution of waterhead incidents is more challenged at the conventional water technology that constantly adopts at present to China.In all kinds of pollution of waterhead things; Organic contamination can not be ignored the harm that people and organism bring, the relatively low organic pollutant of the content of discovered in recent years particularly, as: persistence organic pollutant, DBPs, three cause thing and endocrine disrupter (EDCs) etc.; (carcinogenic, teratogenesis, the mutagenesis) effect that causes because of it has biomagnification property, toxicity, three enjoys all circles' concern with the internal secretion interferon activity; Wherein, endocrine disrupter displays lasting quality/extended residual property, physical chemical characteristics such as biological accumulation property, volatilization/half volatile and high toxicity in the whole ecological working cycle; Compare with the harmful chemical pollutant of other trace toxic; Its toxicity hazard is even more serious, just can be under the situation of trace extremely to organism toxigenicity effect, even harm is of future generation; So also be defined as third generation environmental pollutant, usually as one independently environmental problem be suggested.Research shows; Mostly endocrine disruptor in the natural water body is the phenols incretion obscurant; What often detect has natural estrogen (estrone (E1), 17 beta estradiols (E2)), synthetic estrogen (17 α-lynoral (EE2), diethylstilbestrol (DES)) and an induced by alkyl hydroxybenzene material (NP (4-n-NP)); These pollutents are mainly derived from people and animals' the movement and the bioconversion product of incomplete degraded product, synthetic estrogens medicine and tensio-active agent thereof etc.; Normal not qualified discharge through dirty waste water gets into natural water, is difficult to removed (conventional coagulation, flocculation, precipitation process are lower than 7% and 3% respectively to the clearance of NP and dihydroxyphenyl propane) by current tap water conventional processes
[1], directly be detrimental to health, therefore, it is imperative that the water source that contains this type of organic pollutant science of carrying out is handled.Current to the phenols incretion obscurant remove research more be to adopt high-level oxidation technology and adsorption technology; Wherein the former may produce certain harmful side product (like cholorination by product, bromic acid salts substances etc.) in treating processes; And there is the problem that technical costs is high and existing water factory technological transformation is difficult, so fail to be used widely; For the latter; Then many all the time employing gacs carry out as sorbent material, and it has good effect of removing to water pollutant, has obtained the extensive common recognition of Chinese scholars; Water to current phenols incretion obscurant pollutes, and some research work are also launched in succession.Sun Hongwen etc.
[2]Can fast and effeciently remove the NP of trace in the water through discovering gac; Wang Xiaodong etc.
[3]Investigate ozone and active carbon technology to finding that 30% NP can be removed by ozone oxidation during phenols incretion obscurant removal effect in the water, the residue target compound then can be adsorbed removal by gac fast; Chang etc.
[4]Find that micro-E1 can be adsorbed on the Powdered Activated Carbon well; Fukuhara
[5]Also find when the adsorbability on eight kinds of different commercial gacs of E1 and E2 in the research pure water; When the target compound equilibrium concentration is 1 μ g/L; The adsorptive capacity of E1 is 25.6～73.5mg/g, and the adsorptive capacity of E2 is 21.3～67.6mg/g, shows that these two kinds of target compounds can be well by charcoal absorption; And, cause its adsorbability on gac to exceed 8% than E2 because the hydrophobic nature of E1 is stronger relatively; Choi etc.
[6]Type and the work-ing life of having investigated gac are adsorbed the influence of removing to NP in the water and amerol; Zhang etc.
[7]Studied the removal effect of multiple sorbent material to E1 in the water and E2, wherein the carbon nanotube adsorption ability is the strongest, and gac takes second place, and ion exchange resin, chitosan are the poorest; Yoon etc.
[8]Utilize Powdered Activated Carbon absorption to remove dihydroxyphenyl propane, E2 and EE2 in the water.Because mostly present report is to estimate the adsorbability of typical phenols incretion obscurant on gac, absorption usefulness and gac and other adsorbents adsorb performance comparison of gac; Have only document seldom to consider the influence of type and the work-ing life of gac in the adsorption process to its application; Confirmed directly to affect the absorption property of gac by big quantity research in view of the activated carbon surface physico-chemical property; Therefore be necessary to seek a kind of method of modifying, fundamentally improve and improve the absorption usefulness of gac phenols incretion obscurant in the water.
The public reported relevant with the present invention comprises:
[1]S.G.Kim，K.J.Choi，K.J.Oh.Fate?of?Endocrine?Disruptor?in?Water?Treatment?Processes.IWAWorld?Congress，2002.
[2] Sun Hongwen, Zhai Hongyan, Gao Yuan etc. gac is to the absorption of typical environment endocrine disrupter in the water. water technology, 2005,31 (6): 47～50.
[3] Wang Xiaodong, Zhao Xinhua opens brave. and ozone-active carbon technology is removed typical endocrine disrupter experimental study in the tap water. water supply and drainage, 2006,32 (4): 10～14.
[4]S.Chang，T.D.Waite，P.E.A.One，et?al.Assessment?of?Trace?Estrogenic?ContaminantsRemoval?by?Coagulant?Addition，Powdered?Activated?Carbon?Adsorption?and?PowderedActivated?Carbon/Microfiltration?Processes.Journal?of?Environmental?Engineering，2004，130(7)：736～742.
[5]T.Fukuhara，S.Iwasakia，M.Kawashimab，et?al.Adsorbability?of?Estrone?and?17β-estradiol?inWater?onto?Activated?Carbon.Water?Research，2006，40(2)：241～248.
[6]K.J.Choi，S.G.Kim，C.W.Kim，et?al.Effects?of?Activated?Carbon?Types?and?Service?Lifeon?Removal?of?Endocrine?Disrupting?Chemicals：Amitrol，Nonylphenol，and?Bisphenol-A.Chemosphere，2005，58(11)：1535～1545.
[7]Y.P.Zhang，J.L.Zhou.Removal?of?Estrone?and?17β-Estradiol?from?Water?by?Adsorption.Water?Research，2005，39(16)：3991～4003.
[8]Y.Yoon，P.Westerhoff，S.A.Snyder，et?al.HPLC-fluorescence?Detection?and?Adsorption?ofBisphenol?A，17β-estradiol，and?17a-ethynyl?estradiol?on?Powdered?Activated?Carbon.WaterResearch，2003，37(14)：3530～3537。
(3) summary of the invention
The object of the present invention is to provide a kind of have good adsorption usefulness, long service life and easy regenerated modified activated carbon.The object of the invention also is to provide a kind of preparation method of modified activated carbon.The present invention also aims to provide a kind of modified activated carbon to be used for the treatment process of water middle and high concentration phenols incretion obscurant.
The objective of the invention is to realize like this:
It is that gac is placed in the retort furnace silica tube, and at room temperature earlier with leading to nitrogen 1～2 hour in the retort furnace, gas flow rate is 80～120 ml/min; Afterwards under same nitrogen gas stream protection, retort furnace is warming up to 400～800 ℃ with 10 ℃/minute speed, kept 1～4 hour; After treating that temperature is reduced to 25 ℃; Stop logical nitrogen, continue to take out resulting modified activated carbon with the flow blowing air of 80～120 ml/min 1 hour.
The BET method specific surface area of said gac is 1200～1900m
2/ g, preferred 1300～1700m/g, pore size distribution are at 0.2～50nm, and main peak value is at 1.1～2.0nm and 2.0～4.0nm place; The pore size distribution of said gac is at 0.5～30nm, and the particle size of gac is 0.4～2mm.
The preparation method of modified activated carbon according to the invention is: gac is placed in the retort furnace silica tube, and at room temperature earlier with leading to nitrogen 1～2 hour in the retort furnace, gas flow rate is 80～120 ml/min; Afterwards under same nitrogen gas stream protection, retort furnace is warming up to 400～800 ℃ with 10 ℃/minute speed, kept 1～4 hour; After treating that temperature is reduced to 25 ℃; Stop logical nitrogen, continue to take out and promptly obtain modified activated carbon with the flow blowing air of 80～120 ml/min 1 hour.
The application method of modified activated carbon of the present invention when processing contains phenols incretion obscurant water is: water behind the process conventional filtration or the reactor drum that is filled with modified activated carbon without pretreated former water entering carry out absorption reaction; Modified activated carbon exists with fixed bed form or fluidized-bed form in adsorptive reactor; Control modified activated carbon and 10～30 minutes duration of contact of water, flow velocity is 1～10 meter/hour.
Modified activated carbon of the present invention: be to utilize high temperature inert gas that gac is reduced to handle the back acquisition, be characterized in that surface acidity oxygen-containing functional group content is low, basic group content is high, and it is neutral that iso-electric point is approximately.
The present invention is directed to the drawback that existing conventional water technology and charcoal absorption technology exist; Selected physical structure characteristic absorbent charcoal material is carried out the high temperature nitrogen reduction to be handled; Characterization result shows; Modifying process does not almost change the specific surface area of gac, fully guarantees the absorbent charcoal based ability of removing organic pollutant in the physical structure characteristic in modification front and back.Yet modifying process has changed the chemical property of activated carbon surface significantly; On the one hand; Reduced fully phenols incretion obscurant in the water has been adsorbed disadvantageous acid oxygen-containing functional group content; Obtain a nonpolar stronger carbon surface, promoted the ability of pollutent, further remove through dispersion interaction to this surface diffusion; On the other hand, modifying process also can obviously improve the ratio content that activated carbon surface contains oxonium base property group, impels pollutent to adsorb removal through electron acceptor(EA) donor mode.Therefore; The modified activated carbon absorbent that the present invention obtains; Can be the removal of water middle and high concentration phenols incretion obscurant one optimal adsorption interface is provided; Improve the absorption usefulness of gac greatly, prolong the work-ing life of gac, the treatment process of phenols incretion obscurant in a kind of efficient removal water is provided for the water treatment plant.
The modified activated carbon that the present invention makes can be removed the phenols incretion obscurant of water middle and high concentration effectively; Compare former gac; The modification charcoal has improved 16.1%～22.4% to the removal ability of natural estrogen E1 and E2 in the water; Removal ability to synthetic estrogen EE2 and DES in the water has improved 26.3%～33.5%, and the removal ability of industrial compound 4-n-NP in the water has been improved 25.7%.Mainly owing to the change of activated carbon surface chemical property after the modification, the transformation of particularly carbon surface acid, alkali oxygen-containing functional group content has directly caused gac iso-electric point (pH in the raising of these adsorption effects
PZC) variation, make the pH of modification charcoal
PZCIt is neutral that value is approximately, and eliminated the electrically charged situation of carbon surface in the neutral aqueous solution, strengthened the phenols incretion obscurant and removed in the absorption of carbon surface.The obvious raising of modification charcoal adsorptive power also can prolong the work-ing life of gac greatly, thereby reduces the cost investment of treating processes.Modified activated carbon of the present invention is removed the application method of phenols incretion obscurant in the water as sorbent material; Accomplish through a cover charcoal absorption reactor drum; The practical implementation process is that modified activated carbon is packed in the reactor drum, and charcoal exists with fixed bed form or fluidized-bed form, and the aqueous solution that contains high density phenols endocrine disrupter is handled (or without pre-treatment) through simple conventional filtration; Get into reactor drum; The control residence time of water in active-carbon bed is 10～30 minutes, and flow velocity is 1～10 meter/hour, and the pollutent in the water just can be by absorption removal well at this moment; Water flows out the purpose that reactor drum can reach purification, and this method is particularly suitable for the transformation construction that the existing water factory of China carries out for the water source severe contamination that adapts to current existence.Modification charcoal absorbing phenolic endocrine disrupter water treatment method of the present invention; Has the advantage that operation energy consumption is low, treating processes is not introduced other chemical agents; Be specially adapted to contain the underground water of high toxicity and difficult chemical oxidation organic pollutant and the advanced treatment of surface water; The advanced treatment that also can be used for dirty waste water reduces the concentration that it enters poisonous and harmful organic pollutant in the natural water body, in the treating processes except that organic pollutant being shown efficiently clearance; Also can work in coordination with and remove inorganic pollutants a large amount of in the water and pathogenic micro-organism etc., can improve treating water water quality comprehensively.In addition; The water treatment method of this invention also can be united use with other water technology; As: ozone oxidation-modification charcoal adsorption technology, coupling technique not only can improve removal efficient, the reduction water quality toxicity of total organic carbon in the water, and can improve the removal concentration of solvent borne natural organic matter in the water; Reduce the chlorine-throwed quantity of subsequent disposal and the concentration of chlorine disinfectant product, guarantee effluent quality safety.
(4) embodiment
Embodiment one: the preparation method of the modified activated carbon of this embodiment is following: the gac of particle size between 0.4～2mm placed in the retort furnace silica tube; At room temperature earlier with leading to nitrogen 1.25 hours in the retort furnace, gas flow rate is 100 ml/min, afterwards under same nitrogen gas stream protection; Retort furnace is warming up to 500 ℃ with 10 ℃/minute speed; Kept 3 hours, treat that temperature is reduced to 25 ℃ after, stop logical nitrogen; Continuation is taken out gac and is the modification charcoal with the flow blowing air of 100 ml/min 1 hour.Gac need be used the deionized water repetitive scrubbing before the modification, to the pH value of water constant till, after the modification directly application get final product.
Embodiment two: the water treatment method that modification charcoal of the present invention is used as sorbent material is implemented by following process: the drainage that contains the phenols incretion obscurant after handling through conventional coagulation, deposition, filtration procedure; Get into the inner reactor drum that is filled with modified activated carbon and carry out absorption reaction; Modified activated carbon exists with fixed bed form or fluidized-bed form in adsorptive reactor; Control modified activated carbon and 10～30 minutes duration of contact of water, flow velocity is 1～10 meter/hour.When adopting the fixed bed form; Modified activated carbon need be filled in the reactor drum in advance; The charcoal bed height is between 0.5 meter～1.5 meters, and drainage can have by downflow system, reverse-flow and mix three kinds of modes of streaming and get into reactor drum, and wherein downflow system is that drainage autoreactor below is entered the top and gone out; Reverse-flow is to go out below drainage autoreactor top is advanced; Mixing streaming is the middle part water inlet of charcoal post in the drainage autoreactor, and through adsorbing, filter the back by upper and lower water outlet respectively, the concrete water intake mode of fixed bed form reactor drum can select according to the water treatment field condition; When adopting the fluidized-bed form, modified activated carbon can be from the reactor head reactor drum of packing into, and drainage can only take downflow system to get into from reactor bottom, and the top is filtered and flowed out, and gac is in flow state in reactor drum.
Embodiment three: what this embodiment and embodiment two were different is; Former water is handled without conventional filtration; Directly the adsorptive reactor through the filling modified activated carbon carries out adsorption treatment, and other processing condition are all identical with embodiment two with set-up mode.
Embodiment four: what this embodiment and embodiment two, mode three were different is; The reactor drum of used filling modification charcoal is multistage combined type reactor drum, and its form is a plurality of pipe reactors in series forms, and charcoal exists with the fixed bed form therein; The filling of charcoal highly is 0.5 meter～1.5 meters in each pipe; Former water gets into reactor drum by following current or reflux type, and the control residence time of water in active-carbon bed is 10～30 minutes, and flow velocity is 1～10 meter/hour.This embodiment can guarantee that the effluent quality safety of with serious pollution former water is up to standard.
Embodiment five: this embodiment and embodiment two, mode three are different is to handle or without pretreated former water, at first get into the O3 contacted oxidation tower through simple and regular, and control ozone in water starting point concentration is 0.5～1.5mgO
3/ mgTOC, water is 10～20 minutes at ozone contact dwell time in the tower, water outlet gets in the reactor drum that loads the modification charcoal again and carries out adsorption treatment after the oxidation.This embodiment has the good treatment effect to serious pollution dirt, waste water.
Claims (2)
1. modified activated carbon is characterized in that: it is to be 1300～1700m with BET method specific surface area
2/ g, pore size distribution 0.5～50nm, main peak value at 1.1～2.0nm and 2.0～4.0nm place, when pore size distribution during at 0.5～30nm particle size be that the granulated active carbon of 0.4～2mm places in the retort furnace silica tube; At room temperature earlier with leading to nitrogen 1～2 hour in the retort furnace, gas flow rate is 80～120 ml/min, afterwards under same nitrogen gas stream protection; Retort furnace is warming up to 400～800 ℃ with 10 ℃/minute speed; Kept 1～4 hour, treat that temperature is reduced to 25 ℃ after, stop logical nitrogen; Continuation is taken out resulting modified activated carbon with the flow blowing air of 80～120 ml/min 1 hour.
2. the preparation method of a modified activated carbon, it is characterized in that: with BET method specific surface area is 1300～1700m
2/ g, pore size distribution 0.5～50nm, main peak value at 1.1～2.0nm and 2.0～4.0nm place, when pore size distribution during at 0.5～30nm particle size be that the granulated active carbon of 0.4～2mm places in the retort furnace silica tube; At room temperature earlier with leading to nitrogen 1～2 hour in the retort furnace, gas flow rate is 80～120 ml/min, afterwards under same nitrogen gas stream protection; Retort furnace is warming up to 400～800 ℃ with 10 ℃/minute speed; Kept 1～4 hour, treat that temperature is reduced to 25 ℃ after, stop logical nitrogen; Continuation is taken out and is obtained modified activated carbon with the flow blowing air of 80～120 ml/min 1 hour.
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| CN102951696A (en) * | 2012-11-16 | 2013-03-06 | 内蒙古民族大学 | Application of modified activated carbon in sewage treatment |
| CN106179496B (en) * | 2016-09-21 | 2018-10-16 | 华侨大学 | A kind of preparation method and application of lignin-base hydro-thermal charcoal sulfonic acid catalyst |
| CN108479703A (en) * | 2018-04-18 | 2018-09-04 | 安徽农业大学 | A kind of preparation method for efficiently removing the magnetic active carbon of 17 beta estradiols in water removal |
| CN111659046A (en) * | 2020-06-15 | 2020-09-15 | 北京东瑞科技有限公司 | Protective mask |
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| CN101513999A (en) * | 2009-03-31 | 2009-08-26 | 哈尔滨工程大学 | Active carbon and modification method as well as application thereof in processing water containing endocrine disrupters |
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| CN101513999A (en) * | 2009-03-31 | 2009-08-26 | 哈尔滨工程大学 | Active carbon and modification method as well as application thereof in processing water containing endocrine disrupters |
Non-Patent Citations (1)
| Title |
|---|
| 刘桂芳等.活性炭吸附水中酚类内分泌干扰物试验研究.《中国给水排水》.2008,第24卷(第21期),第52-56页. * |
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