CN104261543B - A kind of coagulant removing humic acid and synthetic method - Google Patents

A kind of coagulant removing humic acid and synthetic method Download PDF

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Publication number
CN104261543B
CN104261543B CN201410548566.8A CN201410548566A CN104261543B CN 104261543 B CN104261543 B CN 104261543B CN 201410548566 A CN201410548566 A CN 201410548566A CN 104261543 B CN104261543 B CN 104261543B
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cnt
coagulant
solution
humic acid
alcl
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CN104261543A (en
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王东升
肖峰
徐慧
葛茂发
于晓琳
姜巍
康东娟
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Institute of Chemistry CAS
Research Center for Eco Environmental Sciences of CAS
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Institute of Chemistry CAS
Research Center for Eco Environmental Sciences of CAS
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen

Abstract

A kind of coagulant removing humic acid, obtains: 1 by the following method) the clean drying of CNT；2)AlCl3Solution adds alkali, prepares the polymeric aluminum chlorides solution that basicity is 2.0；3) by the AlCl of every 60ml1.0mol/L in the polymeric aluminum chlorides solution of step 23Solution adds the ratio addition CNT of 1 2g CNT and reacts.The invention also discloses the method preparing above-mentioned coagulant.Aluminium polychlorid (PACl) is synthesized in carbon nano tube surface by the present invention, improves the coagulant adaptation ability to pH value, and utilizes the absorbability that CNT is good to humic acid, improves coagulation and removes the efficiency of humic acid.The operational approach of the present invention is simple, easy, raw material is easy to get, with low cost, can be widely used in real work.

Description

A kind of coagulant removing humic acid and synthetic method
Technical field
The present invention relates to a kind of coagulant, more particularly to a kind of have efficiently remove humic acid effect Coagulant.
The method that the invention still further relates to prepare above-mentioned coagulant.
Background technology
Humic acid is the Organic substance being widely present in natural water body, and it occupies natural water body The dissolved organic carbon source of 40%-50%, is the important precursor of Disinfection Byproducts in Drinking Water, because of This, the most effectively remove the humic acid in drinking water source, is to ensure that the important work of drinking water quality safety Make.
Minimizing technology currently for humic acid includes coagulation, absorption, membrance separation etc..Wherein adsorb by Easy and simple to handle and with low cost it is widely used in a variety of applications in it.For the removal of pollutant in water body The adsorbing material of application includes Powdered Activated Carbon, chitosan, CNT etc..
CNT, compared with other materials, has the advantages such as bigger draw ratio, resistance to strong acid, highly basic. Additionally, to make CNT have Organic substance good the gap between its internal vestibule and multilamellar carbon pipe Adsorptivity.
In water factory's coagulation process, the flco of formation can occur in the region the most rapid through current Broken, the settleability of the flco after crushing declines, and many results of study show, can not after flco is broken Recover completely.Xu Hui etc. find the flco that Al-based coagulant is formed, and can only show limited reflocculation Ability, this shows that flco shattering process has significant irreversibility.There are some researches show, at pH value Time in neutral range, present in coagulant, nano material is to stirring after end the particle diameter of flco slowly without bright Development rings, but after flco is broken, present in system, nano material has weight to the recovery of flco The impact wanted.Process the flco in humic acid solution processes currently for aluminum system or ferric flocculant to crush Relatively abundant with regrowth process research, but for carbon nano-tube modification aluminium polychlorid (PACl) The process study processing humic acid solution is less.
Summary of the invention
It is an object of the invention to provide a kind of coagulant having and efficiently removing humic acid effect.
It is yet another object of the invention to provide a kind of method preparing above-mentioned coagulant.
For achieving the above object, the coagulant removing humic acid that the present invention provides, can be by following Method obtains:
1) CNT is cleaned and is dried；
2)AlCl3Solution adds alkali, prepares the polymeric aluminum chlorides solution that basicity is 2.0；
3) by the AlCl of every 60ml1.0mol/L in the polymeric aluminum chlorides solution of step 23Solution adds The ratio addition CNT entering 1-2g CNT reacts, and preferred CNT ratio is 1.5-2g。
The method preparing above-mentioned coagulant that the present invention provides, key step is as follows:
1) CNT cleaning, drying；
2)AlCl3Solution adds alkali, prepares the polymeric aluminum chlorides solution that basicity is 2.0；
3) by the AlCl of every 60ml1.0mol/L in the polymeric aluminum chlorides solution of step 23Solution adds The ratio addition CNT entering 1-2g CNT reacts, and preferred CNT ratio is 1.5-2g。
In described method, step 1) in the cleaning process of CNT be included in 0.1mol/L hydrochloric acid Soaking in solution is 24h, utilizes ultra-pure water to clean CNT the most neutral, and forced air drying temperature exists 40 DEG C, blasting time 24h.
In described method, step 2) alkali be Na2CO3。
In described method, step 2) polymeric aluminum chlorides solution be placed in the baking oven of 80 DEG C reaction 16h。
In described method, step 3) reaction be reaction 16h in the baking oven of 80 DEG C.
The invention have the characteristics that
1) introduce in coagulant and there is the CNT of good humic acid removal ability, at coagulation During played the absorbability of CNT.
2) operational approach is simple, and raw material is easy to get, with low cost, and the probability of actual application is relatively Greatly.
3) coagulant after compounding synthesis has good humic acid removal ability.
Accompanying drawing explanation
Fig. 1 is the coagulant building-up process schematic diagram of the present invention.
In Fig. 2, A is modified carbon nanotubes scanning electron microscope (SEM) photograph, and B is energy spectrum analysis figure.
Infrared spectrum characterization before and after A is carbon nano-tube modification in Fig. 3, B is Raman Characterization.
Fig. 4 is the content of the CNT impact on DOC clearance under different DOC content, wherein The pH of A is 5.0, and the pH of B is 7.5, and the pH of C is 9.0.
Fig. 5 is flco change of size under the conditions of different coagulation.
Detailed description of the invention.
Embodiment 1
The coagulant with higher humic acid clearance of the present invention and preparation method, be to be received by carbon Mitron is compounding with Al system coagulant, plays the ability of CNT efficient absorption humic acid, improves The coagulation process clearance to humic acid, for ensureing that good effluent quality provides technical support.
Above-mentioned preparation method comprises the following steps:
1) CNT of purchase is utilized 0.1mol/L soak with hydrochloric acid 24h, remove CNT table The impurity in face, utilizes ultra-pure water to clean CNT to neutrality, dry for standby；
2) AlCl of 1.0mol/L is prepared3Solution, adds alkali, and the present embodiment is with Na2CO3As a example by, Being put into by mixed liquor in reactor and be placed in the baking oven of 80 DEG C reaction 16h, preparing basicity is 2.0 PACl solution (is denoted as PACl (0))；
3) by every 60ml1.0mol/L AlCl in the polymeric aluminum chlorides solution of step 23Solution adds The ratio of 1-2g (preferably 1.5-2g) CNT adds CNT and reacts, and obtains carbon and receives The coagulant of mitron modified PAC l.
Embodiment 2
Humic acid solution is processed with carbon nano-tube modification PACl for coagulant for further illustrating the present invention Effect, investigated the coagulation under different pH value, different content of carbon nanotubes, different DOC content Process, is desirably to obtain carbon nano-tube modification PACl and processes the coagulation property of humic acid.
In order to investigate the different content of carbon nanotubes impact on coagulation process, at the AlCl of 60.0ml3Molten Liquid is simultaneously introduced the CNT of 0.25g, 0.50g, 1.0g, 1.5g, 2.0g, is subsequently adding and makes Standby PACl (0) same amount of Na2CO3, equally mixed liquor is put into the baking oven being placed in 80 DEG C in reactor Middle reaction 16h, the preparation PACl containing different content of carbon nanotubes, be denoted as respectively PACl (1), PACl (2), PACl (3), PACl (4), PACl (5), basicity controls 2.0, in order to not carbon containing The PACl contrast of nanotube.Utilize Ferron method to characterize in the coagulant of preparation, measure wherein Al form.
Under the conditions of different content of carbon nanotubes, Al form is shown in Table 1.
Table 1
Al in table 1aRepresent Al monomer state, AlbRepresent Al13, AlcRepresent Al30。
Along with the increase of content of carbon nanotubes, in coagulant, high polymeric form Al content is improved by 62.04% To 88.4276%, monomer state Al content is reduced to 0.6484% simultaneously, shows that CNT is mixed The building-up process of solidifying agent can effectively reduce AlaDeng monomer state al species, add coagulant Stability.
After the CNT centrifugation in coagulant, deionized water is utilized repeatedly to clean, after drying For characterizing, the method for sign includes: scanning electron microscope, infrared spectrum, Raman spectrum etc..
Fig. 2 is shown in modified carbon nanotubes scanning electron microscope and energy spectrum analysis:
By energy spectrum analysis figure in Fig. 2 it can be seen that the carbon nano tube surface existence in coagulant necessarily contains The aluminum of amount, illustrates that coagulant preparation process aluminum is attached to carbon nano tube surface.
In order to show the Al existing forms in carbon nano tube surface, the CNT after before modified is entered Having gone infrared and Raman Characterization, experimental result is shown in Fig. 3:
Contrast CNTsInfrared spectrum after before modified is it is found that 3450cm-1Place is-OH vibration peak, 1641cm-1The absworption peak at place demonstrates carbon nano tube surface and there is C=C structure, and all peaks are after modification The direction all increased to wavelength is moved, it was demonstrated that Al exists reaction with carbon nano tube surface functional group, Illustrate that Al system coagulant is successfully grafted onto carbon nano tube surface.This experimental selection multi-walled carbon nano-tubes, Using wavelength is the laser excitation of 442nm, it can be seen that be positioned at 1361.7cm on Raman spectrum-1 The D peak of multi-walled carbon nano-tubes, be by caused by the defect in the structure of CNT, be positioned at 1576.8cm-1The G peak of multi-walled carbon nano-tubes, be its characteristic peak.Can from Raman spectrogram Going out, the strength ratio at modified carbon nanotubes D peak and G peak reduces, and depositing of Al in modifying process is described Defect in making CNT reduces.
Six agitating devices are utilized to carry out coagulation experiment, coagulation whipping procedure such as table 2:
Table 2
Water sample through 250rpm stirring 0.5min mix homogeneously after, the coagulant needed for addition, at a slow speed Through the sedimentation of 30min after stirring 10min, measure heavy rear water DOC content.
The DOC content of regulation water sample is 2.0mg/L, 4.0mg/L, 8.0mg/L, is separately added into six kinds Coagulant, coagulation experiment measures heavy rear water DOC after terminating, experimental result is shown in Fig. 4.
From Fig. 4 it is found that along with DOC raises, the clearance of HA is declined by coagulation process, Analyze reason and be that too much HA molecule can make the nano-material surface functional group of addition reach saturated, Make it that clearance of organic molecule to be declined.When DOC content one timing, along with CNTs content Increase, the clearance of DOC presents first increases the trend tended to balance afterwards, due at different CNTs The clearance demonstrating DOC in the experiment of absorption humic acid increases with the increase of content of carbon nanotubes Add, so the cutting mechanisms of humic acid includes the adsorption of CNT and mixes in coagulation process Solidifying agent coagulation removal effect, when the excessive concentration of CNTs, electronegative CNTs can neutralize coagulation The electropositive of agent so that the charge neutrality ability of PACl declines, coagulation effect declines, and removes humic acid Usefulness declines, and should rationally select the dosage of CNT in actual applications, reach treatment effect Optimization with cost.After CNT its area load Al, when pH value is in acid range, The Al of area load will be dissolved as Al3+, form complex, these complex meeting and carbon with HA Nanotube surface produces repulsive interaction thus causes CNT to remove the reduction of humic acid usefulness.Work as pH When value is in alkaline range ,-Al-OH the group of carbon nano tube surface will disappear, and forms a band The surface of negative electricity, produces repulsive interaction with the HA in solution, and in solution, substantial amounts of OH-also can simultaneously The adsorption site limited with HA competition, therefore, under the conditions of acid/base, owing to carbon nano tube surface is special The change of property causes Adsorption humic acid usefulness to reduce.
The humic acid solution that the present embodiment selects DOC content to be 2.0mg/L, regulates the initial of solution PH value is 7.5, and the dosage of coagulant is 0.1mmol/L (in terms of Al), wads a quilt with cotton under the conditions of different coagulations Body is broken sees Fig. 5 with flco change of size situation in regrowth process.
By Fig. 5 it is found that be 2.0mg/L at DOC, when pH value is 7.5, CNT Content for balance time flco particle diameter have no significant effect, but the flco particle diameter after breaking, regenerating length with The increase of the concentration of CNT and increase.Analyze reason to be through modified coagulant effect Mechanism specifically includes that
1, coagulation；
2, the adsorption bridging effect of CNT.
Owing to when pH=7.5, the hydrolytic process of coagulant is relatively more abundant, effect main in system Mechanism is coagulation, therefore the content of CNT has no significant effect for the particle diameter of flco during balance. After the flco formed is broken, due to the bridge linking effect of nano material itself, in flco recovery process Can substantially increase regrowth and terminate the particle diameter of rear flco, improve coagulation effect.
Being shown by data above, (DOC is in 2.0mg/L-4.0mg/L to water former for typical surface water Between, pH value is about 7.5), aluminum chloride with the optimum proportioning of CNT is: every 60ml The AlCl of 1.0mol/L3In solution, content of carbon nanotubes is 1.5g, and its organic clearance can reach To 76.035%, hence it is evident that improve coagulation effect, it is effectively improved the clearance of DOC.If in former water Content of organics is higher, and the content that can properly increase CNT reaches every 60ml1.0mol/L's AlCl3Solution is 2.0g.

Claims (8)

1. remove a coagulant for humic acid, obtain by the following method:
1) CNT is cleaned and is dried；
2)AlCl3Solution adds alkali, prepares the polymeric aluminum chlorides solution that basicity is 2.0；
3) by the AlCl of every 60ml1.0mol/L in the polymeric aluminum chlorides solution of step 23Solution adds The ratio addition CNT entering 1-2g CNT reacts.
Coagulant the most according to claim 1, wherein, step 3) in the ratio of CNT For 1.5-2g.
3. the method for coagulant described in preparation claim 1, key step is as follows:
1) CNT cleaning, drying；
2)AlCl3Solution adds alkali, prepares the polymeric aluminum chlorides solution that basicity is 2.0；
3) by the AlCl of every 60ml1.0mol/L in the polymeric aluminum chlorides solution of step 23Solution adds The ratio addition CNT entering 1-2g CNT reacts.
Method the most according to claim 3, wherein, step 1) in CNT cleaned It is 24h that journey is included in 0.1mol/L hydrochloric acid solution immersion, in utilizing ultra-pure water cleaning CNT extremely Property, forced air drying temperature at 40 DEG C, blasting time 24h.
Method the most according to claim 3, wherein, step 2) alkali be Na2CO3。
Method the most according to claim 3, wherein, step 2) polymeric aluminum chlorides solution put 16h is reacted in the baking oven of 80 DEG C.
Method the most according to claim 3, wherein, step 3) reaction in 80 DEG C Baking oven reacts 16h.
Method the most according to claim 3, wherein, step 3) in the ratio of CNT be 1.5-2g。
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CN1911827A (en) * 2006-09-07 2007-02-14 中国科学院生态环境研究中心 Preparation of nanometer type inorganic polymer flocculant and its product

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CN1911827A (en) * 2006-09-07 2007-02-14 中国科学院生态环境研究中心 Preparation of nanometer type inorganic polymer flocculant and its product

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Coagulation removal of humic acid-stabilized carbon nanotubes from water by PACl:Influences of hydraulic condition and water chemistry;Si Ma et al;《Science of the Total Environment》;20121231;摘要、2.1节及第4节 *
纳米SiO2对微污染物HA、SDS及NH3-N的助凝特性研究;刘春柳等;《环境工程学报》;20111130;第5卷(第11期);第2503-2507页 *

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