CN104587956B - A kind of preparation method being coated with the graphene oxide composite granule coated nano zero valence iron as carrier with multilamellar activated carbon - Google Patents
A kind of preparation method being coated with the graphene oxide composite granule coated nano zero valence iron as carrier with multilamellar activated carbon Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 138
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 46
- 239000008187 granular material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005253 cladding Methods 0.000 claims abstract description 23
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 150000007946 flavonol Chemical class 0.000 claims abstract description 9
- HVQAJTFOCKOKIN-UHFFFAOYSA-N flavonol Natural products O1C2=CC=CC=C2C(=O)C(O)=C1C1=CC=CC=C1 HVQAJTFOCKOKIN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011957 flavonols Nutrition 0.000 claims abstract description 9
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 9
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 9
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000007791 liquid phase Substances 0.000 claims description 15
- 239000007790 solid phase Substances 0.000 claims description 15
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000002250 absorbent Substances 0.000 claims description 7
- 230000002745 absorbent Effects 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 239000003610 charcoal Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- ZUIXQADMAGNCJG-UHFFFAOYSA-M N.[Br-].C(CCC)[P+](CCCC)(CCCC)CCCC Chemical compound N.[Br-].C(CCC)[P+](CCCC)(CCCC)CCCC ZUIXQADMAGNCJG-UHFFFAOYSA-M 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 238000000518 rheometry Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a kind of preparation method with the multilamellar activated carbon cladding graphene oxide composite granule coated nano zero valence iron as carrier, comprise the steps: first to prepare coated nano zero valence iron；Then multilamellar activated carbon cladding graphene oxide composite granule is prepared；The multilamellar activated carbon obtained cladding graphene oxide composite granule is thrown and is added to the water, by preparing graphene oxide suspension after ultrasonic disperse 13 hours, it is subsequently adding prepared coated nano zero valence iron, carry out sucking filtration after being sufficiently stirred for, wash and be dried, obtain being coated with the graphene oxide composite granule coated nano zero-valence iron adsorbent as carrier with multilamellar activated carbon.The present invention prepares coated nano zero valence iron with the most harmless flavonol, bodied ferric sulfate and polyacrylamide for coating material, improves the clearance of heavy metal in water.
Description
Technical field
The present invention relates to the preparation method of a kind of heavy metal absorbent, particularly with the preparation method of the multilamellar activated carbon cladding graphene oxide composite granule coated nano zero valence iron as carrier.
Background technology
At present, China's heavy metal pollution is more serious, and with serious pollution province has had influence on agricultural product and drinking water safety, the area of especially severe, changes basic farmland into town site.How to process heavy metal wastewater thereby, it has also become the focus of Environmental Science and Engineering area research and difficult point, be also the key solving China's heavy metal pollution.Absorption method compared with other method, have easy and simple to handle, the process time is short, low cost, the advantage such as effective, but different adsorbing material is bigger on adsorption effect impact.The adsorbing material of research and development Cheap highly effective, optimize the environmental condition of adsorption process, explore mechanism and the approach of metal ion reuse affecting adsorption process, improve heavy metal ion adsorbed effect, be the key utilizing absorption method to be successfully processed heavy metal wastewater thereby and heavy metal resources.
Nano zero valence iron is strong because of its reducing power, cheaper starting materials is easy to get, the most it is not easily caused secondary pollution, and has the pollutant such as advantage containing halogenated organic matters, nitroaromatic and heavy metal ion etc. efficiently removing in bed mud or water body, have bigger application prospect in field of waste water treatment.
Graphene oxide has Two-dimensional Carbon lamellar structure, and surface area is big, and containing hydroxyl, carbonyl, carboxyl, epoxy radicals isoreactivity oxygen-containing functional group, and these group heavy metal ions have the strongest chelation.On this basis, group modified on research graphene oxide two-dimensional carbon plate Rotating fields, to improving, heavy metal ion adsorbed effect, Selective recognition ability and the heavy metal reclaimed in waste water are significant.
Existing nano zero valence iron the most still has more restriction, is mainly reflected in: the activity of nano zero valence iron is high, and it with the oxygen in water and water reaction, thus can reduce the clearance of target contaminant；Nano zero valence iron activity in acid condition improves, but acid condition can etching apparatus in actual applications；Nano zero valence iron is difficult to reclaim in aqueous, and nano zero valence iron granule is susceptible to reunite in the solution, thus greatly reduces its reactivity and utilization ratio.Although it addition, graphene oxide composite material surface has hydroxyl, carbonyl and carboxyl isoreactivity group, can having an effect with metal ion, but its selectivity be not fully up to expectations.
Summary of the invention
The problem existed for above-mentioned prior art, the present invention provides a kind of preparation method with the multilamellar activated carbon cladding graphene oxide composite granule coated nano zero valence iron as carrier, and the method comprises the steps:
(1) weigh the ferrous sulfate of constant weight, iron sulfate and corresponding sodium borohydride in mortar, grind 10min, it is thus achieved that solid-phase media, standby；
(2) prepare certain density flavonol, bodied ferric sulfate, polyacrylamide mixed aqueous solution as liquid phase medium, standby；
(3) it is 8～15:1 according to the mass ratio of liquid phase medium and solid-phase media, liquid phase medium is added in solid-phase media, stir and be deployed into rheology phase body；React 2h at 20-25 DEG C, by absolute ethanol washing product three times, prepare coated nano zero valence iron, dry for standby in vacuum drying oven；
(4) absorbent charcoal powder body 5 mass parts is added in the reactor, sodium metaaluminate 1 mass parts and tetrabutyl phosphonium bromide ammonia 2 mass parts, then add distilled water, Ludox is added after stirring mixing, at 5.0MPa, stir after 3 hours crystallization 8 hours at 100 DEG C at 40 DEG C, through filtering, wash, drying, obtain activated carbon covered composite yarn powder body；Add Ludox 5 mass parts, tetraethyl ammonium hydroxide 1 mass parts, white carbon 2 mass parts and deionized water 10 mass parts the most in a kettle., stir about obtains mixture gel after 30-60 minute, activated carbon covered composite yarn powder body 5 mass obtained before then adding, graphene oxide 5 mass parts, after stirring mixing, it is incubated 8 hours at 450 DEG C, through cooling, is filtered, washed and dried, obtain multilamellar activated carbon cladding graphene oxide composite granule；
(5) multilamellar activated carbon cladding graphene oxide composite granule step (4) obtained is thrown and is added to the water, by preparing graphene oxide suspension after ultrasonic disperse 1-3 hour, it is subsequently adding the coated nano zero valence iron that step (3) prepares, carry out sucking filtration after being sufficiently stirred for, wash and be dried, obtain being coated with the graphene oxide composite granule coated nano zero-valence iron adsorbent as carrier with multilamellar activated carbon.
Described in step (1), the mass ratio of ferrous sulfate, iron sulfate and sodium borohydride is 1:(1-2): (3～5).
Described in step (2), the mass ratio of flavonol, bodied ferric sulfate and polyacrylamide is 1:(5～12): (2～4).
Multilamellar activated carbon cladding graphene oxide composite granule described in step (5) is 1:1～3 with the mass ratio of coated nano zero valence iron.
The present invention also provide for a kind of use that above-mentioned preparation method obtains with the method for heavy metal ion in the multilamellar activated carbon cladding graphene oxide composite granule coated nano zero valence iron sorbent treatment water as carrier, specific as follows:
Every aqueous solution adds the coated nano zero valence iron that 0.2g～0.8g multilamellar activated carbon cladding graphene oxide composite granule is carrier, the temperature controlling aqueous solution is 20 DEG C～30 DEG C, fully after absorption vibration extremely reaction completely, utilize filter membrane that the remaining liquid after absorption is filtered, complete the removal of heavy metal ion in aqueous solution.
It is an advantage of the current invention that:
(1) present invention prepares coated nano zero valence iron with the most harmless flavonol, bodied ferric sulfate and polyacrylamide for coating material, not only increase water solublity, and prevent nano zero valence iron to react with the oxygen in water and water, thus improve the clearance of target contaminant..
(2) the coated nano zero valence iron with graphene oxide as carrier prepared by the present invention, graphene oxide is linked together by the effect of chemical bond with coated nano zero valence iron, and nano zero valence iron landing will not cause secondary pollution from graphene oxide.
(3) present invention is prepared for graphene oxide composite granule as carrier by the way of cladding, and with the addition of the particulate active charcoal of pore in preparation process respectively, further defines nano/micron pore structure after high temperature removal in the composite.The graphene oxide composite granule absorption property compared with conventional composite powder body using preparation method of the present invention to obtain improves further.It is greatly enhanced through measuring the absorbability of graphene oxide composite granule heavy metal, as the maximal absorptive capacity of Cr6+ is respectively 420 mg/g, being much higher than nano zero valence iron 148 mg/g, the adsorbance of common stannic oxide/graphene nano Zero-valent Iron 162 mg/g, absorbability has been obviously improved 2 times.
(4) not producing the by-product having pollution to environment in the preparation process of the present invention, and raw material is simple and easy to get, preparation cost is relatively low.Preparation technology is simple, and condition is easily-controllable, is suitable to the most large-scale batch production.
Detailed description of the invention
Understandable for enabling the above-mentioned purpose of invention, feature and advantage to become apparent from, below the detailed description of the invention of the present invention is described in detail.
Embodiment 1:
(1) weigh a 1g ferrous sulfate, 2g iron sulfate and 4g sodium borohydride in mortar, grind 10min, it is thus achieved that solid-phase media；
(2) take 1g flavonol, 9g bodied ferric sulfate, 3g polyacrylamide, be dissolved in 30ml water, as liquid phase medium；
(3) it is 12:1 according to the mass ratio of liquid phase medium and solid-phase media, liquid phase medium is added in solid-phase media, stir and be deployed into rheology phase body；At 20 DEG C, react 2h, by absolute ethanol washing product three times, prepare coated nano zero valence iron, dry for standby in vacuum drying oven.
(4) absorbent charcoal powder body 5 mass parts is added in the reactor, sodium metaaluminate 1 mass parts and tetrabutyl phosphonium bromide ammonia 2 mass parts, then add distilled water, Ludox is added after stirring mixing, at 5.0MPa, stir after 3 hours crystallization 8 hours at 100 DEG C at 40 DEG C, through filtering, wash, drying, obtain activated carbon covered composite yarn powder body；Add Ludox 5 mass parts, tetraethyl ammonium hydroxide 1 mass parts, white carbon 2 mass parts and deionized water 10 mass parts the most in a kettle., mixture gel is obtained after stirring 45 minutes, activated carbon covered composite yarn powder body 5 mass obtained before then adding, graphene oxide 5 mass parts, after stirring mixing, it is incubated 8 hours at 450 DEG C, through cooling, is filtered, washed and dried, obtain multilamellar activated carbon cladding graphene oxide composite granule.
(5) multilamellar activated carbon cladding graphene oxide composite granule 10g step (4) obtained is thrown and is added to the water, by preparing graphene oxide suspension after ultrasonic disperse 1-3 hour, it is subsequently adding the coated nano zero valence iron 20g that step (3) prepares, carry out sucking filtration after being sufficiently stirred for, wash and be dried, obtain being coated with the graphene oxide composite granule coated nano zero-valence iron adsorbent as carrier with multilamellar activated carbon.
Every aqueous solution adds 0.5g to modify the rear oxidation Graphene coated nano zero-valence iron adsorbent as carrier；In adsorption process, the temperature controlling aqueous solution is 20 DEG C, fully after absorption vibration extremely reaction completely, utilizes filter membrane to filter, the remaining liquid after absorption to Cu in aqueous solution2+Adsorption rate be 94%, Cr6+Adsorption rate be 97%.
Embodiment 2:
(1) weigh a 1g ferrous sulfate, 2g iron sulfate and 5g sodium borohydride in mortar, grind 10min, it is thus achieved that solid-phase media；
(2) take 1g flavonol, 12g bodied ferric sulfate, 4g polyacrylamide, be dissolved in 30ml water, as liquid phase medium；
(3) it is 15:1 according to the mass ratio of liquid phase medium and solid-phase media, liquid phase medium is added in solid-phase media, stir and be deployed into rheology phase body；At 25 DEG C, react 2h, by absolute ethanol washing product three times, prepare coated nano zero valence iron, dry for standby in vacuum drying oven.
(4) absorbent charcoal powder body 5 mass parts is added in the reactor, sodium metaaluminate 1 mass parts and tetrabutyl phosphonium bromide ammonia 2 mass parts, then add distilled water, Ludox is added after stirring mixing, at 5.0MPa, stir after 3 hours crystallization 8 hours at 100 DEG C at 40 DEG C, through filtering, wash, drying, obtain activated carbon covered composite yarn powder body；Add Ludox 5 mass parts, tetraethyl ammonium hydroxide 1 mass parts, white carbon 2 mass parts and deionized water 10 mass parts the most in a kettle., mixture gel is obtained after stirring 60 minutes, activated carbon covered composite yarn powder body 5 mass obtained before then adding, graphene oxide 5 mass parts, after stirring mixing, it is incubated 8 hours at 450 DEG C, through cooling, is filtered, washed and dried, obtain multilamellar activated carbon cladding graphene oxide composite granule.
(5) multilamellar activated carbon cladding graphene oxide composite granule 10g step (4) obtained is thrown and is added to the water, by preparing graphene oxide suspension after ultrasonic disperse 1-3 hour, it is subsequently adding the coated nano zero valence iron 30g that step (3) prepares, carry out sucking filtration after being sufficiently stirred for, wash and be dried, obtain being coated with the graphene oxide composite granule coated nano zero-valence iron adsorbent as carrier with multilamellar activated carbon.
Every aqueous solution adds 0.2g to modify the rear oxidation Graphene coated nano zero-valence iron adsorbent as carrier；In adsorption process, the temperature controlling aqueous solution is 30 DEG C, fully after absorption vibration extremely reaction completely, utilizes filter membrane to filter, the remaining liquid after absorption to Cd in aqueous solution2+Adsorption rate be 96%, Pb2+Adsorption rate be 92%.
Embodiment 3:
(1) weigh a 1g ferrous sulfate, 1g iron sulfate and 3g sodium borohydride in mortar, grind 10min, it is thus achieved that solid-phase media；
(2) take 1g flavonol, 5g bodied ferric sulfate, 2g polyacrylamide, be dissolved in 30ml water, as liquid phase medium；
(3) it is 8:1 according to the mass ratio of liquid phase medium and solid-phase media, liquid phase medium is added in solid-phase media, stir and be deployed into rheology phase body；At 20 DEG C, react 2h, by absolute ethanol washing product three times, prepare coated nano zero valence iron, dry for standby in vacuum drying oven.
(4) absorbent charcoal powder body 5 mass parts is added in the reactor, sodium metaaluminate 1 mass parts and tetrabutyl phosphonium bromide ammonia 2 mass parts, then add distilled water, Ludox is added after stirring mixing, at 5.0MPa, stir after 3 hours crystallization 8 hours at 100 DEG C at 40 DEG C, through filtering, wash, drying, obtain activated carbon covered composite yarn powder body；Add Ludox 5 mass parts, tetraethyl ammonium hydroxide 1 mass parts, white carbon 2 mass parts and deionized water 10 mass parts the most in a kettle., mixture gel is obtained after stirring 30 minutes, activated carbon covered composite yarn powder body 5 mass obtained before then adding, graphene oxide 5 mass parts, after stirring mixing, it is incubated 8 hours at 450 DEG C, through cooling, is filtered, washed and dried, obtain multilamellar activated carbon cladding graphene oxide composite granule.
(5) multilamellar activated carbon cladding graphene oxide composite granule 10g step (4) obtained is thrown and is added to the water, by preparing graphene oxide suspension after ultrasonic disperse 1-3 hour, it is subsequently adding the coated nano zero valence iron 10g that step (3) prepares, carry out sucking filtration after being sufficiently stirred for, wash and be dried, obtain being coated with the graphene oxide composite granule coated nano zero-valence iron adsorbent as carrier with multilamellar activated carbon.
Every aqueous solution adds 0.8g to modify the rear oxidation Graphene coated nano zero-valence iron adsorbent as carrier；In adsorption process, the temperature controlling aqueous solution is 25 DEG C, fully after absorption vibration extremely reaction completely, utilizes filter membrane to filter, the remaining liquid after absorption to Cr in aqueous solution6+Adsorption rate be 91%, Zn2+Adsorption rate be 93%.
Claims (5)
1. the preparation method being coated with the graphene oxide composite granule coated nano zero valence iron as carrier with multilamellar activated carbon, it is characterised in that the method comprises the steps:
(1) weigh the ferrous sulfate of constant weight, iron sulfate and corresponding sodium borohydride in mortar, grind 10min, it is thus achieved that solid-phase media, standby；
(2) prepare certain density flavonol, bodied ferric sulfate, polyacrylamide mixed aqueous solution as liquid phase medium, standby；
(3) it is 8～15:1 according to the mass ratio of liquid phase medium and solid-phase media, liquid phase medium is added in solid-phase media, stir and be deployed into rheology phase body；React 2h at 20-25 DEG C, by absolute ethanol washing product three times, prepare coated nano zero valence iron, dry for standby in vacuum drying oven；
(4) absorbent charcoal powder body 5 mass parts is added in the reactor, sodium metaaluminate 1 mass parts and tetrabutyl phosphonium bromide ammonia 2 mass parts, then add distilled water, Ludox is added after stirring mixing, at 5.0MPa, stir after 3 hours crystallization 8 hours at 100 DEG C at 40 DEG C, through filtering, wash, drying, obtain activated carbon covered composite yarn powder body；Add Ludox 5 mass parts, tetraethyl ammonium hydroxide 1 mass parts, white carbon 2 mass parts and deionized water 10 mass parts the most in a kettle., mixture gel is obtained after stirring 30-60 minute, activated carbon covered composite yarn powder body 5 mass obtained before then adding, graphene oxide 5 mass parts, after stirring mixing, it is incubated 8 hours at 450 DEG C, through cooling, is filtered, washed and dried, obtain multilamellar activated carbon cladding graphene oxide composite granule；
(5) multilamellar activated carbon cladding graphene oxide composite granule step (4) obtained is thrown and is added to the water, by preparing multilamellar activated carbon cladding graphene oxide suspension after ultrasonic disperse 1-3 hour, it is subsequently adding the coated nano zero valence iron that step (3) prepares, carry out sucking filtration after being sufficiently stirred for, wash and be dried, obtain being coated with graphene oxide composite granule this heavy metal absorbent of coated nano zero valence iron as carrier with multilamellar activated carbon.
Preparation method the most according to claim 1, it is characterised in that described in step (1), the mass ratio of ferrous sulfate, iron sulfate and sodium borohydride is 1:(1-2): (3～5).
Preparation method the most according to claim 1, it is characterised in that described in step (2), the mass ratio of flavonol, bodied ferric sulfate and polyacrylamide is 1:(5～12): (2～4).
Preparation method the most according to claim 1, it is characterised in that the multilamellar activated carbon cladding graphene oxide composite granule described in step (5) is 1:1～3 with the mass ratio of coated nano zero valence iron.
5. one kind use that the arbitrary preparation method of claim 1-4 obtains with the method for heavy metal ion in the multilamellar activated carbon cladding graphene oxide composite granule coated nano zero valence iron adsorption treatment water as carrier, it is characterized in that, every aqueous solution adds the coated nano zero valence iron that 0.2g～0.8g multilamellar activated carbon cladding graphene oxide composite granule is carrier, the temperature controlling aqueous solution is 20 DEG C～30 DEG C, fully after absorption vibration extremely reaction completely, utilize filter membrane that the remaining liquid after absorption is filtered, complete the removal of heavy metal ion in aqueous solution.
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| TWI599402B (en) * | 2016-07-22 | 2017-09-21 | 臺灣塑膠工業股份有限公司 | Submerged-type porous composite carrier, method of producing the same and appliction thereof |
| CN107585802A (en) * | 2017-10-13 | 2018-01-16 | 南京旭羽睿材料科技有限公司 | A kind of graphene composite material applied to Industrial Waste Water Treatments |
| CN108017129B (en) * | 2017-11-29 | 2021-04-20 | 浙江海洋大学 | Composite sewage treatment agent |
| CN109133309A (en) * | 2018-10-10 | 2019-01-04 | 江苏京牧生物技术有限公司 | A kind of preparation method of compound sewage-treating agent |
| CN109316433B (en) * | 2018-12-05 | 2021-08-27 | 邯郸学院 | Skin care mask capable of reducing heavy metal pollution |
| CN110918060A (en) * | 2019-12-16 | 2020-03-27 | 扬州大学 | Pyrolytic carbon-loaded zero-valent iron composite material and preparation method and application thereof |
| CN111334096B (en) * | 2020-03-11 | 2021-08-03 | 浙江理工大学 | Preparation method and product of graphene oxide coated modified carbon black |
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