CN102718279B - Method for removing humic acid pollutants from water by magnetic polyaniline adsorbent - Google Patents
Method for removing humic acid pollutants from water by magnetic polyaniline adsorbent Download PDFInfo
- Publication number
- CN102718279B CN102718279B CN 201210181359 CN201210181359A CN102718279B CN 102718279 B CN102718279 B CN 102718279B CN 201210181359 CN201210181359 CN 201210181359 CN 201210181359 A CN201210181359 A CN 201210181359A CN 102718279 B CN102718279 B CN 102718279B
- Authority
- CN
- China
- Prior art keywords
- water
- humic acid
- sio
- pani
- sorbent material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000004021 humic acid Substances 0.000 title claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 85
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 27
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 27
- 239000003463 adsorbent Substances 0.000 title claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims abstract description 32
- 239000002594 sorbent Substances 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000010521 absorption reaction Methods 0.000 claims description 36
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 230000008929 regeneration Effects 0.000 claims description 9
- 238000011069 regeneration method Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 230000009514 concussion Effects 0.000 claims description 2
- 238000005304 joining Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000009418 renovation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 2
- 239000008213 purified water Substances 0.000 abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 50
- 230000000274 adsorptive effect Effects 0.000 description 14
- 239000002689 soil Substances 0.000 description 7
- 239000011575 calcium Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000008239 natural water Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000031018 biological processes and functions Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- QSKPIOLLBIHNAC-UHFFFAOYSA-N 2-chloro-acetaldehyde Chemical compound ClCC=O QSKPIOLLBIHNAC-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- GHXZTYHSJHQHIJ-UHFFFAOYSA-N Chlorhexidine Chemical compound C=1C=C(Cl)C=CC=1NC(N)=NC(N)=NCCCCCCN=C(N)N=C(N)NC1=CC=C(Cl)C=C1 GHXZTYHSJHQHIJ-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229960003260 chlorhexidine Drugs 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for removing humic acid pollutants from water by magnetic polyaniline adsorbent, which comprises the following steps: adding magnetic Fe3O4@SiO2-PANI as an adsorbent into to-be-purified water body, wherein the mass magnetic Fe3O4@SiO2-PANI is 0.0004-0.0008 times more than the mass of water, utilizing the magnetic Fe3O4@SiO2-PANI to adsorb the humic acid pollutants in the water for 1.0min to 24h under the situations that the temperature is 15-35 degrees centigrade; pH value is 2.0-10.0; and concentration of Ca2<+> is 0-20 mmol/L; in external magnetic field, separating the adsorbent from the adsorption system to obtain the purified water body without the humic acid pollutants. The method takes Fe3O4@SiO2-PANI as the adsorbent, which is significantly better than the adsorption performance of traditional adsorption materials (such as activated carbon). The method is simple to operate and has low cost.
Description
Technical field
The invention belongs to the water body purification processing technology field, relate to the method for removing humic acid in the water body, particularly a kind of magnetic polyaniline sorbent material Fe that utilizes
3O
4@SiO
2-PANI removes the method for humic acid pollutants in the water.
Background technology
Humic acid is the macromole poly-ring aromatic compounds of multiple functional groups such as a kind of phenolic hydroxy group, carboxyl, alcoholic extract hydroxyl group, is a kind of important reductive organic matter in the water body, is a kind of organic colloid of complexity.Soil ulmin in the natural water body derives from agron lower-molecular-weight component, waterplant and low etc. planktonic decomposition, accounts for 50%～90% of total organic matter in the water.Humic acid in the water body can cause various environment and health problem.Humic acid can produce offending color and smell in water body.Humic acid is easily with chlorhexidine-containing disinfectant reaction generation is multiple that toxic byproduct arranged in the water, as trichloromethane, chloracetic acid, chlorinated phenol, chloro ketone, chloro aldehyde etc., these by products become the little object that pollutes strict control in drinking water source to the effect that the people has " carcinogenic, teratogenesis, mutagenesis ".Humic acid ionization in water forms electronegative anionoid polymerization ionogen, the contained multiple functional group in surface can carry out complex reaction with the metal ion that coexists in the water or interact with other organic pollutant, formation has the polymer substance of complex construction, cause combined pollution, influence migration and the conversion in water of heavy metal and organic pollutant, increased the degree of difficulty of administering; Humic acid is similar sponge structure in the pH value near time neutral, this structure causes it to have very big interior external surface area, top oxygen-containing functional group can capture inorganic and organic small molecules, so the normal part of the small organic molecule in the natural water body is attracted on the humic acid molecule; Humic acid can be adsorbed on the surface of colloid and suspended substance (clay, bacterium, virus, algae etc.), strengthens electronegativity, the stability and dispersed of these particulate matter.Therefore how efficiently removing humic acid in the water becomes the focus of current environment research.
At present, be used for the acid-treated method of water humic and mainly contain biological process, flocculence, membrane filtration and chemical catalytic oxidation method etc.But because humic acid itself is difficult to by biological degradation, the film that potential safety hazard, the membrane filtration that flocculation agent exists exists that the water-soluble humic acid of small molecular weight is difficult to remove, calcium, the isoionic influence of magnesium cause in the natural water body pollutes and the restriction of economic dispatch condition, and chemical catalytic oxidation running cost height, device is complicated, treatment capacity is limited.The limitation of traditional treatment method highlights day by day, therefore, presses for a kind of safer, treatment process efficiently.Absorption method has good application prospects as the treatment process of less energy-consumption, high security, also more and more is subjected to people's attention.
The advantage of absorption method is that the organism of the reluctant metal ion of biological process and difficult degradation is had treatment effect preferably.Generally speaking, have bigger specific surface area and high pore volume on the sorbent material, be conducive to obtain adsorption efficiency efficiently, it also can form various chemical bonds by the various active groups in surface and adsorbate, reaches the organic purpose of enrichment selectively.Use maximum sorbent materials at present acticarbon, resin sorbent are arranged.And there is certain problem in acticarbon in application process, soil ulmin can pass through electric charge mass transfer, hydrogen bond action, hydrophobic interaction formation macromole complex compound in solution, these macromole complex compounds may cause the duct of gac to stop up in the process that forms, thereby stop more soil ulmin to enter gac inside; And macroporous adsorbent resin is not good to the hydrophilic small molecules organism adsorption effect in the soil ulmin, and the salt resistance of absorbent resin has much room for improvement and the production cost height.
In the soil ulmin water treatment procedure, amino class sorbent material is widely used, all be common amino class sorbing material as chitosan, polyacrylamide and aminoresin, its carboxyl and phenolic hydroxyl group that relies on the protonated amino of adsorbent surface and humic acid to dissociate forms mixture, thereby reaches the purpose of removing humic acid in the water.
In recent years, the synthetic of conducting polymer become one of Materials science important field of research, and the environmental stability of polyaniline is good, chemical property is stable, specific conductivity controllability height, synthesis technique are simply ripe, and the humic acid in the water body is had avidity preferably.Contain a large amount of amino and imino group in the polyaniline molecule, can with water in heavy metal ion, organic pollutant generation complexing or redox reaction, and then the pollution substance in the removal water, but therefore the saturated back of its absorption and the water body separation difficulty that desire purifies have hindered its application.
Superparamagnetic nanomaterial is the research focus of material in recent years, and it not only has the big specific surface area of nano material, stronger surface energy, and high surfactivity, and have strong magnetic, it is separated easily.Superparamagnetic nanomaterial is made up of magnetic core and the polymer shell that is rich in activity.Magnetic core is made of magnetic nano-particle usually, and the oxide compound of iron is (as Fe
3O
4) nanoparticle has high magnetic intensity and superparamagnetism, is often used as the nuclear of magnetic adsorbent.Silicon-dioxide is received to have than high chemical stability, can be used as polymer shell.
At present, magnetic Nano material is commonly used for the sorbent treatment water pollutant aspect water surrounding, and as heavy metal, dyestuff etc., but the organism report is fewer in the planar water.The early-stage Study discovery of this seminar, polyaniline sorbent material have soil ulmin in the water adsorbs removal effect preferably, but absorption back sorbent material separation difficulty, therefore, the synthesizing magnetic polyaniline material, and use it for the removal of soil ulmin, can effectively solve and separate difficult problem.Humic acid pollutants yet there are no report in the magnetic polyaniline sorbent material removal water and utilize.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing magnetic polyaniline sorbent material to remove humic acid pollutants in the water, this method is utilized magnetic Fe
3O
4@SiO
2Except anhydrating middle humic acid pollutants, sorbent material separates with water body-PANI easily as sorbent material, and can use repeatedly behind wash-out, and purification rate is high and simple to operate, with low cost.
For achieving the above object, the present invention has adopted following technical scheme:
Add water the magnetic polyaniline sorbent material of 0.0004～0.0008 times of physique amount in the water body that purifies to desire, utilize the humic acid pollutants in the magnetic polyaniline adsorbents adsorb water body, the magnetic polyaniline sorbent material in the water body is collected in the absorption back under the effect of externally-applied magnetic field, then magnetic polyaniline sorbent material is separated the purifying water body that has obtained removing humic acid pollutants with water body.
The starting point concentration of humic acid pollutants is 4.5～52mg/L in the water body that described desire purifies.
The water body that described desire purifies places encloses container, externally-applied magnetic field is the magnet that is placed on the encloses container lower end, (guaranteeing that selected strong magnets surface area can cover the encloses container floorage), under externally-applied magnetic field magnetic guiding, the sorption of magnetic polyaniline sorbent material is in the encloses container bottom.
Described magnetic polyaniline sorbent material is Fe
3O
4@SiO
2-PANI.
Described Fe
3O
4@SiO
2The preparation method of-PANI is:
1) with FeCl
36H
2O and FeCl
24H
2O be dissolved in after according to 2: 1 mixed in molar ratio in the hydrochloric acid of 0.1～0.5mol/L mixed solution A; in 1.0～1.5mol/L NaOH aqueous solution, drip mixed solution A while stirring then; the volume ratio of mixed solution A and the NaOH aqueous solution is 1: 9; dropwise back aging reaction 1～2h under 80～85 ℃, nitrogen protection condition and get the solid synthetics, with the solid synthetics with deionized water wash after under 40～50 ℃ of conditions vacuum drying obtain Fe
3O
4
2) with dehydrated alcohol and deionized water according to 4: 1 volume ratio mix mixing solutions B, with Fe
3O
4Successively with joining after 0.05～0.1mol/L hydrochloric acid, the washed with de-ionized water among the mixing solutions B, ultrasonic 25～the 30min of water-bath then, adding massfraction after water-bath is ultrasonic at ambient temperature while stirring and be 28～30% ammoniacal liquor makes pH reach 11, drip tetraethoxy (TEOS) then, every 0.5g Fe
3O
4Need to add the 1.0mL tetraethoxy, under 50～60 ℃ of conditions, stir 11～12h behind the adding tetraethoxy and get throw out, throw out filtration, cleaning, drying are obtained Fe
3O
4@SiO
2
3) with Fe
3O
4@SiO
2With aniline join successively in the deionized water mixture, Fe
3O
4@SiO
2With the mass ratio of aniline be 3: 2; adding massfraction in the mixture while stirring and be 35% hydrochloric acid makes pH reach 3; add hydrochloric acid afterreaction 1～2h; be cooled to 0～5 ℃ then; add ammonium persulfate aqueous solution after the cooling while stirring; aniline is 1: 2～2: 1 with the amount of substance ratio of ammonium persulphate, and polyreaction 6～7h under nitrogen protection obtains Fe with throw out filtration, cleaning, drying after polyreaction is finished then
3O
4@SiO
2-PANI.
Described Fe
3O
4@SiO
2-PANI takes off absorption under alkaline condition, realize regeneration.
Described Fe
3O
4@SiO
2The renovation process of-PANI is: the Fe that will be adsorbed with humic acid pollutants
3O
4@SiO
2-PANI places 0.01～0.05mol/L NaOH aqueous solution concussion 10～12h under 15～25 ℃ to take off absorption, the NaOH aqueous solution and Fe
3O
4@SiO
2The mass ratio of-PANI is 1500～2000:1, and the Fe after the absorption is taken off in collection
3O
4@SiO
2It is neutral to pH for several times that-PANI, water clean, and can reuse.
The temperature of water body is that 15～35 ℃, pH are 2.0～10.0 in the described adsorption process, Ca in the water body
2+The concentration of ion is 0～20mmol/L, and adsorption time is 1.0min～24h.
Compared with prior art, the present invention has following beneficial technical effects:
The present invention is with magnetic polyaniline sorbent material Fe
3O
4@SiO
2-PANI absorption is also removed humic acid pollutants in the water body, magnetic polyaniline sorbent material shows the absorption property that obviously is better than traditional sorbing material (as gac), improved purification rate, simultaneously because the magnetic that magnetic polyaniline sorbent material itself has, its separation is quite easy, therefore, the present invention has simple to operate, advantage with low cost.
Further, Fe
3O
4@SiO
2The maximal absorptive capacity of-PANI is 36.53mg/g, and the maximal absorptive capacity of gac is 2.51mg/g, with Fe
3O
4@SiO
2-PANI is as sorbent material, and adsorption rate is fast, and 2～3h just can reach adsorption equilibrium, and low pH and high Ca
2+Ionic concn is of value to the absorption of humic acid in the water.And collection Fe
3O
4@SiO
2Behind-the PANI, utilize NaOH solution to carry out Fe
3O
4@SiO
2The desorption of-PANI (taking off absorption), after desorption is finished, Fe
3O
4@SiO
2-PANI can recycle; And the regeneration rate that takes off for the first time absorption is 76.8%, and the absorption regeneration experiment is adsorbed, taken off in circulation, regenerates after five times, and the regeneration rate that takes off absorption is 80.6%, takes off the absorption regeneration rate and remains unchanged substantially.The present invention is with Fe
3O
4@SiO
2-PANI is used for micro-polluted water, and (starting point concentration is that 4mg/L～51mg/L) removal of humic acid pollutants has good economic benefit and environmental benefit.The humic acid pollutants starting point concentration is in the water of 4.5mg/L, and the humic acid clearance reaches more than 90.4%; Starting point concentration is in the water of 23mg/L, and the humic acid clearance reaches about 62.2%; Starting point concentration is in the water of 51mg/L, and the humic acid clearance reaches about 35%.
Embodiment
The present invention is described in further detail below in conjunction with the detection of specific embodiment and humic acid removal effect, and the explanation of the invention is not limited.
Embodiment 1
Fe as sorbent material
3O
4@SiO
2-PANI, present embodiment specifically adopt chemical oxidization method to synthesize:
With 0.04mol FeCl
36H
2O and 0.02mol FeCl
24H
2Be dissolved in after O mixes and get mixed solution A in the 50ml0.5mol/L hydrochloric acid; in the 450ml 1.5mol/L NaOH aqueous solution, drip mixed solution A while stirring then; dropwise back aging reaction 1h under 80 ℃, nitrogen protection condition and get the solid synthetics, with the solid synthetics with deionized water wash after under 50 ℃ of conditions vacuum drying obtain Fe
3O
4
With 0.5g Fe
3O
4Successively through 0.1mol/L hydrochloric acid, join after going dried up cleaning among the mixing solutions B that 240ml dehydrated alcohol and 60ml deionized water form, the ultrasonic 30min of water-bath then, ultrasonic power is 80kW, adding massfraction after water-bath is ultrasonic at ambient temperature while stirring and be 28～30% ammoniacal liquor makes pH reach 11, drip 1.0mL tetraethoxy (TEOS) then, under 50 ℃ of conditions, stir 12h behind the adding tetraethoxy and get throw out, will obtain Fe after throw out filtration, cleaning, the drying
3O
4@SiO
2
With 0.3g Fe
3O
4@SiO
2With 0.2g aniline join successively in the 50ml deionized water mixture; adding massfraction in the mixture while stirring and be 35% hydrochloric acid makes pH reach 3; add hydrochloric acid afterreaction 1h; be cooled to 0～5 ℃ then; add while stirring after the cooling ammonium persulfate aqueous solution (with the 0.26g ammonium persulphate be dissolved in the 2ml deionized water ammonium persulfate aqueous solution); polyreaction 6h under nitrogen protection obtains Fe with throw out filtration, cleaning, drying after polyreaction is finished then
3O
4@SiO
2-PANI.
With Fe
3O
4@SiO
2-PANI is as sorbent material, and handling humic acid pollution starting point concentration is the contaminated water of 27.9mg/L, and this contaminated water is mixed by humic acid pollutants and deionized water.For the ease of the calculating of clearance, will contain the water that humic acid pollutes and be placed in the closed container, add the Fe that contains 0.0005 times of quality that humic acid pollutes then in the closed container
3O
4@SiO
2-PANI adds Fe
3O
4@SiO
2The pH of water body is 5～6 behind the-PANI, and 25 ℃ of constant temperature vibration absorption, adsorption time is 24h, collects Fe behind the absorption 24h then
3O
4@SiO
2-PANI, the adsorptive capacity that records humic acid is 31.36mg/g, the clearance of humic acid is 56.19%.The absorption of humic acid refers to the content of every gram adsorbents adsorb humic acid, and the clearance of humic acid refers to the humic acid concentration that is adsorbed and the ratio of starting point concentration.
Embodiment 2
With embodiment 1, with Fe
3O
4@SiO
2-PANI is as sorbent material, and adsorption conditions is 15 ℃ of constant temperature vibration absorption, and other conditions are constant, and the adsorptive capacity that records humic acid is 23.34mg/g, and clearance is 42.65%.
Embodiment 3
With embodiment 1, with Fe
3O
4@SiO
2-PANI is as sorbent material, and adsorption conditions is 35 ℃ of constant temperature vibration absorption, and other conditions are constant, and the adsorptive capacity that records humic acid is 36.95mg/g, and clearance is 66.55%.
As seen, under the same terms, along with the rising of temperature, the adsorptive capacity of humic acid and clearance all increase accordingly.
Embodiment 4
With embodiment 1, with Fe
3O
4@SiO
2-PANI is as sorbent material, and adsorption time is 10min in the adsorption conditions, and other conditions are constant, and the adsorptive capacity that records humic acid is 12.32mg/g, and the clearance of humic acid is 22.08%;
Embodiment 5
With embodiment 1, with Fe
3O
4@SiO
2-PANI is as sorbent material, and adsorption time is 616min in the adsorption conditions, and other conditions are constant, and the adsorptive capacity that records humic acid is 14.15mg/g, and the clearance of humic acid is 49.29%;
This shows that before absorption reached balance, the adsorptive capacity of humic acid increased gradually along with the increase of time, and adsorption time is more long, the clearance of humic acid is more high.
Embodiment 6
With embodiment 1, with Fe
3O
4@SiO
2-PANI in the adsorption conditions, is 2(acidic conditions with pH regulator as sorbent material), other conditions are constant, and the adsorptive capacity that records humic acid is 52.02mg/g, and the clearance of humic acid is 94.16%;
With embodiment 1, with Fe
3O
4@SiO
2-PANI in the adsorption conditions, is 6.0 with pH regulator as sorbent material, and other conditions are constant, and the adsorptive capacity that records humic acid is 28.47mg/g, and the clearance of humic acid is 51.28%;
With embodiment 1, with Fe
3O
4@SiO
2-PANI in the adsorption conditions, is 9.1(alkaline condition with pH regulator as sorbent material), other conditions are constant, and the adsorptive capacity that records humic acid is 12.99mg/g, and the clearance of humic acid is 23.27%;
This shows Fe
3O
4@SiO
2The adsorptive capacity of humic acid reduces along with the rising of pH in the water of-PANI, and low pH is conducive to the removal of humic acid in the water.
Embodiment 7
With embodiment 1, with Fe
3O
4@SiO
2-PANI is as sorbent material, in the adsorption conditions, and Ca in water
2+Concentration is carried out for the 2.5mmol/L condition, and other conditions are constant, and the adsorptive capacity that records humic acid is 50.92mg/g, and the clearance of humic acid is 92.17%; Work as Ca
2+When concentration reached 15mmol/L, other conditions were constant, and the adsorptive capacity that records humic acid is 52.24mg/g, and the clearance of humic acid is 93.5%.
This shows Fe
3O
4@SiO
2The absorption of humic acid raises along with the increase of ionic strength in the water of-PANI.
Embodiment 8
With embodiment 1, after adsorption equilibrium, collect Fe
3O
4@SiO
2-PANI is desorbing agent with the 0.01mol/L NaOH aqueous solution, takes off absorption in closed container, 15～25 ℃ of constant temperature vibrations, the NaOH aqueous solution and Fe
3O
4@SiO
2The mass ratio of-PANI is 1500～2000: 1, takes off adsorption time 10～12h, and it is 76.8% that mensuration is taken off adsorption rate (taking off adsorption rate is humic acid quality and the adsorbent humic acid mass ratio that takes off absorption) for the first time.Taking off absorption back sorbent material with washed with de-ionized water for several times, is neutral to pH, carries out adsorption experiment again, and experiment condition is with embodiment 1.Absorption regeneration experiment is adsorbed, is taken off in circulation, regenerate after five times, and taking off absorption regeneration rate (taking off the absorption regeneration rate is this absorption humic acid quality and the humic acid mass ratio that adsorbs for the first time of sorbent material) is 80.6%.
This shows Fe
3O
4@SiO
2Humic acid absorption can be taken off absorption after saturated in the water of-PANI in the NaOH of 0.01mol/L solution, regenerates that adsorptive capacity remains unchanged substantially after five times, shows that this sorbent material has better recyclability, can be recycled.
Embodiment 9
With embodiment 1, with Fe
3O
4@SiO
2Be sorbent material, humic acid is not had tangible adsorption.This shows that the polyaniline on the magnetic adsorbent has played key effect to the adsorption of humic acid.
Claims (6)
1. method of utilizing magnetic polyaniline sorbent material to remove humic acid pollutants in the water, it is characterized in that: may further comprise the steps: the magnetic polyaniline sorbent material that adds water 0.0004～0.0008 times of physique amount in the water body that purifies to desire, utilize the humic acid pollutants in the magnetic polyaniline adsorbents adsorb water body, the magnetic polyaniline sorbent material in the water body is collected in the absorption back under the effect of externally-applied magnetic field, then magnetic polyaniline sorbent material is separated the purifying water body that has obtained removing humic acid pollutants with water body, described magnetic polyaniline sorbent material is Fe
3O
4@SiO
2-PANI, described Fe
3O
4@SiO
2The preparation method of-PANI is:
1) with 0.04mol FeCl
36H
2O and 0.02mol FeCl
24H
2Be dissolved in after O mixes and get mixed solution A in the 50ml0.5mol/L hydrochloric acid; in 1.0～1.5mol/L NaOH aqueous solution, drip mixed solution A while stirring then; the volume ratio of mixed solution A and the NaOH aqueous solution is 1:9; dropwise back aging reaction 1～2h under 80～85 ℃, nitrogen protection condition and get the solid synthetics, with the solid synthetics with deionized water wash after under 40～50 ℃ of conditions vacuum drying obtain Fe
3O
4
2) 240ml dehydrated alcohol and 60ml deionized water are mixed mixing solutions B, with 0.5g Fe
3O
4With joining after 0.05～0.1mol/L hydrochloric acid, the washed with de-ionized water among the mixing solutions B, the ultrasonic 25～30min of water-bath adds ammoniacal liquor at ambient temperature while stirring and makes pH reach 11 after water-bath is ultrasonic then, drips tetraethoxy then, every 0.5g Fe successively
3O
4Need to add the 1.0mL tetraethoxy, under 50～60 ℃ of conditions, stir 11～12h behind the adding tetraethoxy and get throw out, throw out filtration, cleaning, drying are obtained Fe
3O
4@SiO
2
3) with Fe
3O
4@SiO
2With aniline join successively in the deionized water mixture, Fe
3O
4@SiO
2With the mass ratio of aniline be 3:2; adding hydrochloric acid while stirring in the mixture makes pH reach 3; add hydrochloric acid afterreaction 1～2h; be cooled to 0～5 ℃ then; add ammonium persulfate aqueous solution after the cooling while stirring; aniline is 1:2～2:1 with the amount of substance ratio of ammonium persulphate, and polyreaction 6～7h under nitrogen protection obtains Fe with throw out filtration, cleaning, drying after polyreaction is finished then
3O
4@SiO
2-PANI.
2. according to the described a kind of method of utilizing magnetic polyaniline sorbent material to remove humic acid pollutants in the water of claim 1, it is characterized in that: the starting point concentration of humic acid pollutants is 4.5～52mg/L in the water body that described desire purifies.
3. according to the described a kind of method of utilizing magnetic polyaniline sorbent material to remove humic acid pollutants in the water of claim 1, it is characterized in that: the water body that described desire purifies places encloses container, externally-applied magnetic field is the magnet that is placed on the encloses container lower end, under externally-applied magnetic field magnetic guiding, the sorption of magnetic polyaniline sorbent material is in the encloses container bottom.
4. according to the described a kind of method of utilizing magnetic polyaniline sorbent material to remove humic acid pollutants in the water of claim 1, it is characterized in that: described Fe
3O
4@SiO
2-PANI takes off absorption under alkaline condition, realize regeneration.
5. according to the described a kind of method of utilizing magnetic polyaniline sorbent material to remove humic acid pollutants in the water of claim 1, it is characterized in that: described Fe
3O
4@SiO
2The renovation process of-PANI is: the Fe that will be adsorbed with humic acid pollutants
3O
4@SiO
2-PANI places 0.01～0.05mol/L NaOH aqueous solution concussion 10～12h under 15～25 ℃ to take off absorption, the NaOH aqueous solution and Fe
3O
4@SiO
2The mass ratio of-PANI is 1500～2000:1, and the Fe after the absorption is taken off in collection
3O
4@SiO
2It is neutral to pH for several times that-PANI, water clean, and can reuse.
6. according to the described a kind of method of utilizing magnetic polyaniline sorbent material to remove humic acid pollutants in the water of claim 1, it is characterized in that: the temperature of water body is that 15～35 ℃, pH are 2.0～10.0 in the described adsorption process, Ca in the water body
2+The concentration of ion is 0～20mmol/L, and adsorption time is 1.0min～24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210181359 CN102718279B (en) | 2012-06-05 | 2012-06-05 | Method for removing humic acid pollutants from water by magnetic polyaniline adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210181359 CN102718279B (en) | 2012-06-05 | 2012-06-05 | Method for removing humic acid pollutants from water by magnetic polyaniline adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102718279A CN102718279A (en) | 2012-10-10 |
| CN102718279B true CN102718279B (en) | 2013-08-28 |
Family
ID=46944188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210181359 Expired - Fee Related CN102718279B (en) | 2012-06-05 | 2012-06-05 | Method for removing humic acid pollutants from water by magnetic polyaniline adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102718279B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101354268B1 (en) * | 2011-12-28 | 2014-02-07 | 경북대학교 산학협력단 | Preparation method of granular oxide absorbents and water treatment method using the same |
| CN103933954A (en) * | 2014-04-24 | 2014-07-23 | 陕西科技大学 | Preparation method of magnetic polypyrrole and method of adsorbing nitrate in water |
| CN103920473B (en) * | 2014-04-28 | 2015-10-28 | 扬州大学 | The preparation method of carbon modifying titanium dioxide composite magnetic nano adsorber |
| CN103920537A (en) * | 2014-04-28 | 2014-07-16 | 扬州大学 | Method for preparing magnetic polyaniline noble metal nanometer catalyst |
| CN105056887B (en) * | 2015-08-06 | 2018-06-29 | 广东工业大学 | A kind of magnetic carbon-nano tube composite material of negative Ca and preparation method and application |
| CN105140018B (en) * | 2015-08-21 | 2017-08-11 | 浙江大学 | A kind of preparation method of magnetic high-molecular nanosphere |
| CN105903453A (en) * | 2016-06-06 | 2016-08-31 | 陕西科技大学 | Preparation method of EDTA modified magnetic adsorbent and method for removing trivalent chromium in water |
| CN106540656A (en) * | 2016-09-22 | 2017-03-29 | 华东交通大学 | It is a kind of to have magnetic Fe3O4The preparation method of base magnetic crust charcoal new adsorbent |
| CN106914228A (en) * | 2017-04-28 | 2017-07-04 | 长乐净能新材料科技有限公司 | A kind of novel magnetic composite nano materials and its application |
| CN109979762A (en) * | 2019-04-23 | 2019-07-05 | 桂林理工大学 | A kind of preparation method of porous ferroferric oxide/carbon composite electrode material |
| CN110170303A (en) * | 2019-06-10 | 2019-08-27 | 陕西科技大学 | A kind of heavy-metal adsorption material and its preparation method and application |
| CN111320986B (en) * | 2020-03-27 | 2021-11-09 | 浙江易承环境科研有限公司 | Soil remediation technology |
| CN111715195A (en) * | 2020-06-22 | 2020-09-29 | 武汉科技大学 | Copper slag polyaniline magnetic composite adsorbent and preparation method thereof |
| CN114873819A (en) * | 2022-05-27 | 2022-08-09 | 安徽理工大学环境友好材料与职业健康研究院(芜湖) | Multi-pollutant sewage magnetic treatment system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008049315A (en) * | 2006-08-28 | 2008-03-06 | Sumitomo Seika Chem Co Ltd | Adsorbent for gold and method for recovering gold by selective separation |
| CN101928048A (en) * | 2010-08-27 | 2010-12-29 | 陕西科技大学 | Method for purifying humic acid pollutants in water by utilizing polyaniline |
| CN102360659A (en) * | 2011-06-24 | 2012-02-22 | 中国科学院宁波材料技术与工程研究所 | Magnetic submicron composite core-shell particles, and preparation method and application thereof |
-
2012
- 2012-06-05 CN CN 201210181359 patent/CN102718279B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008049315A (en) * | 2006-08-28 | 2008-03-06 | Sumitomo Seika Chem Co Ltd | Adsorbent for gold and method for recovering gold by selective separation |
| CN101928048A (en) * | 2010-08-27 | 2010-12-29 | 陕西科技大学 | Method for purifying humic acid pollutants in water by utilizing polyaniline |
| CN102360659A (en) * | 2011-06-24 | 2012-02-22 | 中国科学院宁波材料技术与工程研究所 | Magnetic submicron composite core-shell particles, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102718279A (en) | 2012-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102718279B (en) | Method for removing humic acid pollutants from water by magnetic polyaniline adsorbent | |
| Zhou et al. | Adsorption behavior of tetracycline from aqueous solution on ferroferric oxide nanoparticles assisted powdered activated carbon | |
| Khulbe et al. | Removal of heavy metals and pollutants by membrane adsorption techniques | |
| Khandaker et al. | Functionalized layered double hydroxides composite bio-adsorbent for efficient copper (II) ion encapsulation from wastewater | |
| CN103418340B (en) | Reduction-oxidation graphene-Fe3O4 nano composite, preparation method thereof, and application of reduction-oxidation graphene-Fe3O4 nano composite in absorbing bisphenol A | |
| Liu et al. | Modification of bio-char derived from fast pyrolysis of biomass and its application in removal of tetracycline from aqueous solution | |
| Liang et al. | Synthesis of a novel three-dimensional porous carbon material and its highly selective Cr (VI) removal in wastewater | |
| Ji et al. | Dynamic adsorption of Cu (II) from aqueous solution by zeolite/cellulose acetate blend fiber in fixed-bed | |
| CN101805037B (en) | Method for removing humic acid pollutants in water by magnetic chitosan particle | |
| CN105903438B (en) | A kind of attapulgite and the compound adsorbent and preparation method thereof of graphene oxide | |
| CN105251448B (en) | A kind of preparation method of magnetic graphene composite | |
| CN110237820B (en) | Preparation method and application of microwave-assisted magnetic hollow Zn/Co zeolite imidazole nanocage material | |
| CN103611494A (en) | Amido modified attapulgite clay adsorbent and method for preparing and adsorbing humic acid | |
| CN103861866A (en) | Fixed enrichment method for city life compost heavy metals through modified nanocarbon | |
| CN102233259A (en) | Adsorbent for removing heavy metal from water and preparation method of adsorbent | |
| Gao et al. | N-propyl functionalized spherical mesoporous silica as a rapid and efficient adsorbent for steroid estrogen removal: Adsorption behaviour and effects of water chemistry | |
| CN103357375B (en) | Magnetic mesoporous silica adsorbent for removing organic pollutants in water body and preparation method and application thereof | |
| Osman et al. | Advanced adsorbents for ibuprofen removal from aquatic environments: a review | |
| CN102008942B (en) | Method for removing tannic acid pollutant from aminated magnetic nano composite particles | |
| CN102277742A (en) | Preparation method of cleaning material of heavy metal ions in reusable water | |
| CN103962108A (en) | Method for removing hexavalent chromium in water by utilizing polyethyleneimine modified graphite oxide | |
| CN102367182A (en) | Method for treating waste water with organic modified bentonite | |
| Mahmoud et al. | A novel multifunctional sandwiched activated carbon between manganese and tin oxides nanoparticles for removal of divalent metal ions | |
| Sun et al. | The influential factors towards graphene oxides removal by activated carbons: Activated functional groups vs BET surface area | |
| Kumar et al. | Removal of heavy metals and radionuclides from water using nanomaterials: current scenario and future prospects |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130828 |