CN103357375A - Magnetic mesoporous silica adsorbent for removing organic pollutants in water body and preparation method and application thereof - Google Patents
Magnetic mesoporous silica adsorbent for removing organic pollutants in water body and preparation method and application thereof Download PDFInfo
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- CN103357375A CN103357375A CN2013103096675A CN201310309667A CN103357375A CN 103357375 A CN103357375 A CN 103357375A CN 2013103096675 A CN2013103096675 A CN 2013103096675A CN 201310309667 A CN201310309667 A CN 201310309667A CN 103357375 A CN103357375 A CN 103357375A
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- organic pollutants
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000003463 adsorbent Substances 0.000 title claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 37
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000012265 solid product Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 235000014413 iron hydroxide Nutrition 0.000 claims abstract description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims abstract description 3
- 238000000746 purification Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229960004887 ferric hydroxide Drugs 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 5
- -1 sucrose fatty ester Chemical class 0.000 claims description 5
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001213 Polysorbate 20 Polymers 0.000 claims 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 238000003911 water pollution Methods 0.000 abstract description 2
- 239000002250 absorbent Substances 0.000 abstract 2
- 230000002745 absorbent Effects 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- 238000003756 stirring Methods 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000003643 water by type Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 9
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 description 6
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 6
- 229910016874 Fe(NO3) Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- GGMPTLAAIUQMIE-UHFFFAOYSA-N 2,3,4,5,6-pentachlorobiphenyl Chemical group ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=CC=CC=C1 GGMPTLAAIUQMIE-UHFFFAOYSA-N 0.000 description 3
- 229960003276 erythromycin Drugs 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229960003511 macrogol Drugs 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
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- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 241000894007 species Species 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention provides a magnetic mesoporous silica adsorbent for removing organic pollutants in a water body and a preparation method and an application thereof and belongs to the technical field of material synthesis and water pollution control. The preparation method comprises the following steps: carrying out a reaction between ferric salt and alkali in water, centrifuging, adding an acetic acid solution into an iron hydroxide precipitate containing bound water, and stirring until a hydrated iron oxide colloidal solution is formed; adding a non-ionic soluble organic macromoleclar polymer and a silicon-source precursor, stirring until the polymer and the precursor are completely mixed, collecting a generated solid product after a hydrothermal reaction, drying and roasting to obtain the magnetic mesoporous silica adsorbent. The absorbent has a good adsorption effect on organic pollutants in a water body, especially macromolecular organic pollutants. After adsorption and saturation, the absorbent can be rapidly separated from the water body by the application of a magnetic field. Magnetic substances are wrapped in mesoporous silica and will not drop from mesoporous silica. The magnetic mesoporous silica adsorbent can be used in water purification.
Description
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Technical field
The invention belongs to the synthetic technical field of water pollution control that reaches of material, relate to a kind of magnetic mesoporous silica adsorbent and preparation and application thereof of removing Organic Pollutants In Water.
Background technology
Along with the organic chemistry industrial expansion, organic compound is used widely at aspects such as medicine, process hides, electronics and agricultural chemicals, causes intermediate product or byproduct in large weight organic compounds and the building-up process to be discharged in the environment in large quantities.Organic Pollution in China's water body environment is very serious, kind is many, quantity is large, the organic matter that jeopardizes health reaches two, 300 kind, this pollutant is exposed in the environment enduringly, can bring huge threat to environment and human health that we depend on for existence.Wherein the some organic pollutants chemical property is relatively stable, easily accumulates in the organic matter of organism, soils and sediments, and in occurring in nature degraded slowly, the environmental hazard cycle is long, the effect of many being considered to have " carcinogenic, teratogenesis shape, mutagenesis ".Human this limited water resource is subject to day by day serious pollution, in waterworks feedwater process, removes the organic pollution in the water body, becomes an important process such as phenols, halogenated hydrocarbons, agricultural chemicals, Polychlorinated biphenyls, nitrosamine, antibiotic, humic acid etc.
At present, divide according to handling principle, the processing method of Organic Pollutants In Water mainly can be divided into physical method (absorption method, extraction, membrane processing method) and chemical method (Fenton reagent and Ozonation, photocatalytic method, chemical reduction method, ultrasonic method).Although the research of at present relevant Organic Pollutants In Water biodegrading process is own through obtaining larger progress, but also exist reaction rate slow, cost is high, and product is complicated, cause secondary pollution problems, research and develop new and effective, safe, nontoxic removal and biodegrading process extremely urgent.
Because most organic pollutions can be adsorbed agent absorption at aqueous phase, can reach the purpose that effective removal is reclaimed, and have the plurality of advantages such as the efficient of removal is high, easy and simple to handle, cost is low.In recent years, some expert has reported and has utilized active carbon, polymer resin etc., removes the organic pollution of aqueous phase, but these material poor heat stability, the recycling rate is low, and because the aperture is less, relatively poor to the absorption property of large molecular organic pollutants.Researching and developing novel effective organic pollutant removal material urgently can not treat.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of preparation method who removes the magnetic mesoporous silica adsorbent of Organic Pollutants In Water with not enough.
Another object of the present invention is to provide the magnetic mesoporous silica adsorbent for preparing by said method.
A further object of the present invention is to provide the application of above-mentioned magnetic mesoporous silica adsorbent.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method who removes the magnetic mesoporous silica adsorbent of Organic Pollutants In Water comprises the steps:
(1) react in water by molysite and alkali, make iron hydroxide, centrifugal after, in the ferric hydroxide precipitate that includes in conjunction with water, add glacial acetic acid, and be stirred to and form hydrated ferric oxide colloidal solution;
(2) in hydrated ferric oxide colloidal solution, add nonionic soluble organic macromolecule polymer and silicon source presoma, be stirred to fully and mix, hydro-thermal reaction 2～48 hours, collect the solid product that generates, the be removed magnetic mesoporous silica adsorbent of Organic Pollutants In Water of oven dry, roasting.
Molysite described in the step (1) is preferably ferric nitrate or iron chloride.
Alkali described in the step (1) is preferably NaOH or sodium carbonate.
The mol ratio of the glacial acetic acid described in the step (1) and ferro element is 2～20: 1.
Nonionic soluble high-molecular organic matter described in the step (2) is preferably AEO, Pluronic F108, polyethylene glycol, polyvinyl alcohol or sucrose fatty ester.
The mass ratio of the nonionic soluble high-molecular organic matter described in the step (2) and hydrated ferric oxide colloidal solution is preferably 1: 2.5～and 100.
Silicon source presoma described in the step (2) is preferably ethyl orthosilicate, methyl silicate, Ludox or waterglass.
The mol ratio of element silicon and ferro element is preferably 2～20 in the step (2): 1.
Described in the step (2) the temperature of hydro-thermal reaction be preferably 40～180 ℃.
Collection described in the step (2) is preferably by centrifugal or filtration and collects.
The atmosphere of the roasting described in the step (2) is preferably nitrogen or inert gas, such as argon gas, helium etc.; The temperature of roasting is preferably 200～800 ℃.
A kind of magnetic mesoporous silica adsorbent of removing Organic Pollutants In Water prepares by said method.
The above-mentioned magnetic mesoporous silica adsorbent of removing Organic Pollutants In Water has preferably adsorption effect to the organic pollution in the water body, can be used for purification of water quality.
The present invention compared with prior art has following advantage:
(1) magnetic species and silica presoma be by hydro-thermal reaction generation polycondensation, thereby be wrapped in the mesopore silicon oxide, and separation can not come off in the use procedure.
(2) magnetic mesoporous silica adsorbent can be efficiently the Some Organic Pollutants, particularly large molecular organic pollutants in the adsorbed water rapidly, process thoroughly, adsorption capacity is large, this material of every gram can adsorb organic pollution more than 50 milligrams.
(3) this adsorbent is easy to use, after adsorbent absorption is saturated, can realize Separation of Solid and Liquid under the effect of externally-applied magnetic field.
Description of drawings
Fig. 1 is the magnetization curve figure of the magnetic mesoporous silica adsorbent of embodiment 1 preparation.
Fig. 2 is the X-ray diffraction spectrogram of the magnetic mesoporous silica adsorbent of embodiment 1 preparation.
Fig. 3 is the nitrogen adsorption/desorption isotherm of the magnetic mesoporous silica adsorbent of embodiment 1 preparation.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is done further detailed description, but embodiments of the present invention are not limited to this.
Embodiment 1
1.62 gram Fe(NO3)39H2Os are dissolved in 18 ml pure waters, 0.64 gram NaOH is dissolved in 10 ml pure waters, mix above-mentioned two kinds of solution, with precipitation and centrifugal separation, be 0.32% acetum (mol ratio of acetic acid molecule and ferro element is 2:1) to including in conjunction with adding 15 milliliters of mass concentrations in the ferric hydroxide precipitate of water, and be stirred to formation hydrated ferric oxide colloidal solution.The mass ratioes that add 7.2 gram Pluronic F108 these copolymers of P123(and hydrated ferric oxide colloidal solution in this colloidal solution are about 1:2.5) and 1.67 restrain ethyl orthosilicates (element silicon and ferro element mol ratio are 2:1), be stirred to fully and mix, 40 ℃ of reactions of hydro-thermal 2 hours; The solid product that generates is centrifugal, oven dry, then 500 ℃ of roastings 2 hours in nitrogen namely obtain magnetic mesoporous silica-based adsorbent.The magnetization curve of this adsorbent shows that it has magnetic (as shown in Figure 1) in magnetic field, and the X-ray diffraction structural analysis shows that the main magnetisable material of material is Fe
3O
4(as shown in Figure 2), N
2Absorption/desorption isotherm meets according to IUPAC (IUPAC) definition
The type adsorption isotherm illustrates that this material has meso-hole structure.In the erythromycin solution of 10 milliliter of 10 mg/litre, add 10 milligrams of these adsorbents, the erythromycin in the solution can be adsorbed fully through 0.5 hour; Solution after the absorption is placed magnetic field, adsorbent and solution can be separated in 5 minutes.This adsorbent of every gram can adsorb the phenol in the water more than 60 milligrams, the N-nitrosamino group dimethylamine more than 50 milligrams and the erythromycin more than 100 milligrams.
10.8 gram ferric chloride hexahydrates are dissolved in 180 ml pure waters, 8.5 gram sodium carbonate are dissolved in 100 ml pure waters, mix above-mentioned two kinds of solution, with precipitation and centrifugal separation, be 8.0% acetum (acetic acid molecule and ferro element mol ratio are 5:1) to including in conjunction with adding mass concentration in the ferric hydroxide precipitate of water, and be stirred to formation hydrated ferric oxide colloidal solution.The mass ratioes that add 9.0 gram Pluronic F108 these materials of F127(and hydrated ferric oxide colloidal solution in this colloidal solution are about 1:20) and 30.4 restrain methyl silicates (element silicon and ferro element mol ratio are 5:1), be stirred to fully and mix, 60 ℃ of reactions of hydro-thermal 10 hours; The solid product that generates is centrifugal, oven dry, then 200 ℃ of roastings 2 hours in helium namely obtain magnetic mesoporous silica-based adsorbent.In the DDT solution of 10 milliliter of 15 mg/litre, add 10 milligrams of these adsorbents, the DDT in the solution can be adsorbed fully through 0.5 hour; Solution after the absorption is placed magnetic field, adsorbent and solution can be separated in 5 minutes.This adsorbent of every gram can adsorb the o-chlorphenol in the water more than 60 milligrams, the DDT more than 70 milligrams, the pentachlorodiphenyl more than 70 milligrams and the ammonium humate more than 90 milligrams.
Embodiment 3
16.2 gram Fe(NO3)39H2Os are dissolved in 180 ml pure waters, 6.4 gram NaOH are dissolved in 100 ml pure waters, mix above-mentioned two kinds of solution, with precipitation and centrifugal separation, be 12.8% acetum (acetic acid molecule and ferro element mol ratio are 8:1) to including in conjunction with adding mass concentration in the ferric hydroxide precipitate of water, and be stirred to formation hydrated ferric oxide colloidal solution.In this colloidal solution, add 4.5 gram AEOs (molecular weight 1200, the mass ratio of this material and hydrated ferric oxide colloidal solution is about 1:40) and 64 gram Ludox (SiO
2Content is 30%, and element silicon and ferro element mol ratio are 8:1), be stirred to fully and mix, 80 ℃ of reactions of hydro-thermal 18 hours; The solid product that generates is centrifugal, oven dry, then 400 ℃ of roastings 2 hours in argon gas namely obtain magnetic mesoporous silica-based adsorbent.Add 10 milligrams of these adsorbents in the pentachlorophenol solution of 10 milliliter of 10 mg/litre, can make through 0.5 hour that the clearance of pentachlorophenol reaches 90% in the solution; Solution after the absorption is placed magnetic field, adsorbent and solution can be separated in 5 minutes.This adsorbent of every gram can adsorb the pentachlorophenol in the water and the pentachlorodiphenyl more than 70 milligrams more than 50 milligrams.
Embodiment 4
16.2 gram Fe(NO3)39H2Os are dissolved in 180 ml pure waters, 6.4 gram NaOH are dissolved in 100 ml pure waters, mix above-mentioned two kinds of solution, with precipitation and centrifugal separation, be 19.0% acetum (acetic acid molecule and ferro element mol ratio are 12:1) to including in conjunction with adding mass concentration in the iron oxide precipitation of water, and be stirred to formation hydronium(ion) oxidation iron colloidal solution.Adding 3.0 gram Macrogol 6000s (polyethylene glycol and hydrated ferric oxide colloidal solution mass ratio are about 1:60) and 58.56 in this colloidal solution, to restrain waterglass (be sodium metasilicate, element silicon and ferro element mol ratio are 12:1), be stirred to fully and mix, 100 ℃ of reactions of hydro-thermal 26 hours; The solid product that generates is centrifugal, oven dry, then 300 ℃ of roastings 2 hours in helium namely obtain magnetic mesoporous silica-based adsorbent.In the ROX solution of 10 milliliter of 10 mg/litre, add 10 milligrams of these adsorbents, the ROX in the solution can be adsorbed fully through 0.5 hour; Solution after the absorption is placed magnetic field, adsorbent and solution can be separated in 5 minutes.This adsorbent of every gram can adsorb DDT and the ROX more than 80 milligrams more than 60 milligrams.
Embodiment 5
16.2 gram Fe(NO3)39H2Os are dissolved in 180 ml pure waters, 6.4 gram NaOH are dissolved in 100 ml pure waters, mix above-mentioned two kinds of solution, with precipitation and centrifugal separation, with precipitation and centrifugal separation, be 25.3% acetum (acetic acid molecule and ferro element mol ratio are 16:1) to including in conjunction with adding 150 milliliters of mass concentrations in the iron oxide precipitation of water, and be stirred to formation hydrated ferric oxide colloidal solution.The mass ratio that adds 0.11 gram PVAC polyvinylalcohol-1788(polyvinyl alcohol and hydrated ferric oxide colloidal solution in this colloidal solution is about 1:80) and 97.4 restrain methyl silicates (element silicon and ferro element mol ratio are 16:1), be stirred to fully and mix, 140 ℃ of reactions of hydro-thermal 36 hours; The solid product that generates is centrifugal, oven dry, then 600 ℃ of roastings 2 hours in nitrogen namely obtain magnetic mesoporous silica-based adsorbent.In the N-nitrosamino group dimethylamine solution of 10 milliliter of 10 mg/litre, add 10 milligrams of these adsorbents, can make the clearance of N-nitrosamino group dimethylamine in the solution reach 95% through 0.5 hour; Solution after the absorption is placed magnetic field, adsorbent and solution can be separated in 5 minutes.This adsorbent of every gram can adsorb pentachlorodiphenyl more than 70 milligrams and the N-nitrosamino group dimethylamine more than 50 milligrams.
Embodiment 6
16.2 gram Fe(NO3)39H2Os are dissolved in 180 ml pure waters, 6.4 gram NaOH are dissolved in 100 ml pure waters, mix above-mentioned two kinds of solution, with precipitation and centrifugal separation, be 31.5% acetum (acetic acid molecule and ferro element mol ratio are 20:1) to including in conjunction with adding 150 milliliters of mass concentrations in the iron oxide precipitation of water, and be stirred to formation hydrated ferric oxide colloidal solution.In this colloidal solution, add 1.82 gram sucrose fatty ester (HLB values 11.0, acid number 5mg KOH/g, the mass ratio of itself and hydrated ferric oxide colloidal solution is about 1:100) and 97.6 gram waterglass (be sodium metasilicate, element silicon and ferro element mol ratio are 20:1), be stirred to fully and mix, 180 ℃ of reactions of hydro-thermal 48 hours; The solid product that generates is centrifugal, oven dry, then 800 ℃ of roastings 2 hours in nitrogen namely obtain magnetic mesoporous silica-based adsorbent.In the ammonium humate solution of 10 milliliter of 10 mg/litre, add 10 milligrams of these adsorbents, the ammonium humate in the solution can be adsorbed fully through 0.5 hour; Solution after the absorption is placed magnetic field, adsorbent and solution can be separated in 5 minutes.This adsorbent of every gram can adsorb DDT and the ammonium humate more than 80 milligrams more than 60 milligrams.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method who removes the magnetic mesoporous silica adsorbent of Organic Pollutants In Water is characterized in that comprising the steps:
(1) react in water by molysite and alkali, make iron hydroxide, centrifugal after, in the ferric hydroxide precipitate that includes in conjunction with water, add acetum, and be stirred to and form hydrated ferric oxide colloidal solution;
(2) in hydrated ferric oxide colloidal solution, add nonionic soluble organic macromolecule polymer and silicon source presoma, be stirred to fully and mix, hydro-thermal reaction 2～48 hours, collect the solid product that generates, the be removed magnetic mesoporous silica adsorbent of Organic Pollutants In Water of oven dry, roasting.
2. the preparation method who removes the magnetic mesoporous silica adsorbent of Organic Pollutants In Water according to claim 1, it is characterized in that: the molysite described in the step (1) is ferric nitrate or iron chloride; Alkali described in the step (1) is NaOH or sodium carbonate.
3. the preparation method who removes the magnetic mesoporous silica adsorbent of Organic Pollutants In Water according to claim 1, it is characterized in that: the nonionic soluble high-molecular organic matter described in the step (2) is AEO, polyoxyethylene sorbitan monolaurate, Pluronic F108, polyethylene glycol, polyvinyl alcohol or sucrose fatty ester.
4. the preparation method who removes the magnetic mesoporous silica adsorbent of Organic Pollutants In Water according to claim 1, it is characterized in that: the mass ratio of the nonionic soluble high-molecular organic matter described in the step (2) and hydrated ferric oxide colloidal solution is 1: 2.5～100.
5. the preparation method who removes the magnetic mesoporous silica adsorbent of Organic Pollutants In Water according to claim 1, it is characterized in that: the silicon source presoma described in the step (2) is ethyl orthosilicate, methyl silicate, Ludox or waterglass.
6. the preparation method who removes the magnetic mesoporous silica adsorbent of Organic Pollutants In Water according to claim 1 is characterized in that: the mol ratio of element silicon and ferro element is 2～20: 1 in the step (2).
7. the preparation method who removes the magnetic mesoporous silica adsorbent of Organic Pollutants In Water according to claim 1 is characterized in that: described in the step (2) the temperature of hydro-thermal reaction be 40～180 ℃.
8. the preparation method who removes the magnetic mesoporous silica adsorbent of Organic Pollutants In Water according to claim 1, it is characterized in that: the atmosphere of the roasting described in the step (2) is nitrogen or inert gas, the temperature of roasting is 200～800 ℃.
9. a magnetic mesoporous silica adsorbent of removing Organic Pollutants In Water is characterized in that: prepare by each described method of claim 1-8.
10. the application of magnetic mesoporous silica adsorbent in purification of water quality of removing Organic Pollutants In Water claimed in claim 9.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084124A (en) * | 2014-06-18 | 2014-10-08 | 中国地质大学（北京） | Biochar adsorbent for petroleum organic pollutants, and preparation method and application thereof |
| CN104211126A (en) * | 2014-09-17 | 2014-12-17 | 湖南大学 | Iron-carrying meso-porous silicon composite material as well as preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887705A (en) * | 2005-06-30 | 2007-01-03 | 中国科学院生态环境研究中心 | Prepn process of organic pillared interlayered clay material |
| KR20080084315A (en) * | 2007-03-16 | 2008-09-19 | 엘지마이크론 주식회사 | Magnetism nano particle coated silica and method for manufacturing thereof |
| CN101485969A (en) * | 2008-06-23 | 2009-07-22 | 南京工业大学 | Supercritical method for preparing nano Fe3O4/SiO2Method of compounding aerogel particles |
| CN102727488A (en) * | 2012-06-29 | 2012-10-17 | 陈士忠 | Clathrate compound of mesoporous silica/Fe3O4 magnetic nanometer complex and oxaprozin |
-
2013
- 2013-07-23 CN CN201310309667.5A patent/CN103357375B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887705A (en) * | 2005-06-30 | 2007-01-03 | 中国科学院生态环境研究中心 | Prepn process of organic pillared interlayered clay material |
| KR20080084315A (en) * | 2007-03-16 | 2008-09-19 | 엘지마이크론 주식회사 | Magnetism nano particle coated silica and method for manufacturing thereof |
| CN101485969A (en) * | 2008-06-23 | 2009-07-22 | 南京工业大学 | Supercritical method for preparing nano Fe3O4/SiO2Method of compounding aerogel particles |
| CN102727488A (en) * | 2012-06-29 | 2012-10-17 | 陈士忠 | Clathrate compound of mesoporous silica/Fe3O4 magnetic nanometer complex and oxaprozin |
Non-Patent Citations (3)
| Title |
|---|
| IAN J. BRUCE ET AL.: "Synthesis, characterisation and application of silica-magnetite nanocomposites", 《JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS》, vol. 284, 2 August 2004 (2004-08-02) * |
| 朱霞萍 等: "四氧化三铁/二氧化硅复合磁性纳米粒子的制备与表征", 《精细石油化工》, vol. 27, no. 4, 31 July 2010 (2010-07-31) * |
| 赵紫来 等: "氧化铁磁性纳米粒子的制备、表面修饰及在分离和分析中的应用", 《化学进展》, vol. 18, no. 10, 31 October 2006 (2006-10-31) * |
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