CN106861635A - 磁性介孔氧化硅吸附剂及制备方法与其在去除水体中有机物和重金属复合污染中的应用 - Google Patents
磁性介孔氧化硅吸附剂及制备方法与其在去除水体中有机物和重金属复合污染中的应用 Download PDFInfo
- Publication number
- CN106861635A CN106861635A CN201710158776.XA CN201710158776A CN106861635A CN 106861635 A CN106861635 A CN 106861635A CN 201710158776 A CN201710158776 A CN 201710158776A CN 106861635 A CN106861635 A CN 106861635A
- Authority
- CN
- China
- Prior art keywords
- preparation
- mesoporous silica
- alkaline solution
- iron salt
- magnetic mesoporous
- 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.)
- Pending
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 30
- 239000003463 adsorbent Substances 0.000 title claims abstract description 18
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 12
- 239000005416 organic matter Substances 0.000 title description 8
- 239000002905 metal composite material Substances 0.000 title description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000012670 alkaline solution Substances 0.000 claims abstract description 21
- 150000002505 iron Chemical class 0.000 claims abstract description 17
- 125000003368 amide group Chemical group 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005642 Oleic acid Substances 0.000 claims abstract description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 8
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 239000012467 final product Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000006249 magnetic particle Substances 0.000 claims description 9
- 238000003911 water pollution Methods 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 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
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 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 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- 239000003921 oil Substances 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- -1 γ-aminopropyl Chemical group 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 239000004098 Tetracycline Substances 0.000 description 9
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 9
- 229960003742 phenol Drugs 0.000 description 9
- 229940063650 terramycin Drugs 0.000 description 9
- 229960002180 tetracycline Drugs 0.000 description 9
- 229930101283 tetracycline Natural products 0.000 description 9
- 235000019364 tetracycline Nutrition 0.000 description 9
- 150000003522 tetracyclines Chemical class 0.000 description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical class O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明公开了一种磁性介孔氧化硅吸附剂，它是向铁盐溶液中加入油酸、含CTAB的碱性溶液，反应后再加入含CTAB的碱性溶液、硅源前驱体和胺基试剂，经升温反应即得。本发明还公开了前述磁性介孔氧化硅吸附剂的制备方法与应用。与现有技术相比，本发明既可以通过模板剂疏水段提供的位点吸附分子态的微污染有机物，又可以通过胺基试剂提供的位点吸附溶液中的重金属离子，可以同时高效净化复合污染水体。同时，本发明方法工业简单，流程较短，具有极高的效率。
Description
技术领域
本发明属于水体净化领域，具体涉及磁性介孔氧化硅吸附剂及制备方法与其在去除水体中微污染有机物和重金属离子中的应用。
背景技术
随着我国工农业的发展、人口激增和社会经济的快速发展，大量的污染物质伴随着生活生产过程被排放到环境水体中，造成日益严重的水体污染。然而，当前环境中的污染物正趋于多元化和复杂化，进入生态系统中的污染物的种类随时间呈指数增长，环境污染不再是单一污染的理想状态，而是以由各种污染物构成的复合污染为主，这为污染水体的治理提出了新的挑战。目前单一类型污染和同类型污染物复合污染的废水已基本能够有效处理。但有机污染物与重金属离子复合污染导致的水体污染特性和生物毒性的变化致使该类复合污染废水仍难以得到有效治理。
介孔氧化硅由于具有长程有序性、高度的结构和表面性能可调节性、孔径大小(2-30nm)和孔道结构可控性、较大的比表面积和高孔隙率等特点，在有机物和重金属离子的去除中均具有较好的应用。然而传统的介孔氧化硅在实际应用中，存在吸附分离困难、运行成本高、操作复杂等缺陷。为了提高吸附剂的分离性能，减少吸附剂的流失，不少研究者尝试在吸附剂内部负载磁性纳米颗粒使其具有优异的分离性能(H.Tian,etal.J.Hazard.Mater.2009,171(1-3):459-464.)。然而目前磁性介孔氧化硅材料基本上仅仅只对有机物(S.Tao,et al.Micropor.Mesopor.Mat.,2012,147:295-301.)或者只对重金属离子(Walcarius A.,et al.,J.Mater.Chem.,2012,20,4478-4511.)具有较好的去除效果。而对被有机污染物与重金属离子复合污染的水体，净化效果很差。因此，为了解决该问题，亟待开发出一种新的对复合污染水体中大量微污染有机物和重金属同时具有高效去除效果的磁性介孔氧化硅。
发明内容
本发明公开了一种磁性介孔氧化硅吸附剂，以解决现有介孔氧化硅对复合污染水体中大量微污染有机物和重金属同时去除效果差的问题。
本发明还公开了上述磁性介孔氧化硅吸附剂的制备方法。
本发明最后公开了上述磁性介孔氧化硅吸附剂在去除水体污染中的应用。
为解决上述技术问题，本发明采用的技术方案如下：
一种磁性介孔氧化硅吸附剂的制备方法，它包括如下步骤：
(1)向铁盐溶液中滴加油酸和含CTAB的碱性溶液，60～80℃下反应30～120min；
(2)(2)利用外加磁铁分离步骤(1)中所得混合体系，得到的磁性粒子和液体部分，将磁性粒子与含CTAB的碱性溶液、硅源前驱体、胺基试剂混合，搅拌完全后升温至60～80℃反应2～8h，收集反应所得固体产物，清洗后烘干，即得。
步骤(1)中，所述的铁盐溶液和碱性溶液的溶剂均为去氧纯净水。
步骤(1)和(2)中，所述的碱性溶液为氨水或者氢氧化钠的水溶液。
步骤(1)中，所述的铁盐溶液中包括二价铁盐和三价铁盐；其中，所述的二价铁盐为氯化亚铁、硫酸亚铁或硝酸亚铁，三价铁盐为氯化铁、硫酸铁或硝酸铁。
步骤(1)中，二价铁盐、三价铁盐、油酸、碱性溶液中碱和CTAB的摩尔比为1：2～4：0.5～2：4～16：0.1～1；其中，所述的碱性溶液中碱是指氨水中的氨气或氢氧化钠的水溶液中的氢氧化钠。
步骤(2)中，所述的碱性溶液为氨水或者氢氧化钠的水溶液。
步骤(2)中，所述的硅源前驱体为正硅酸乙酯或正硅酸甲酯，所述的胺基试剂为γ―氨丙基三乙氧基硅烷和/或γ-氨丙基三甲氧基硅烷。
步骤(2)中，CTAB、碱性溶液中碱、硅源前驱体和胺基试剂的摩尔比为1：1.5～3：5～9：1～3。
步骤(2)中，磁性粒子的质量为步骤(2)中含CTAB的碱性溶液、硅源前驱体和胺基试剂总质量的5～15％。
步骤(2)中，烘干温度为60℃。
上述制备方法中任意一项制备得到的磁性介孔氧化硅吸附剂也在本发明的保护范围之内。
上述磁性介孔氧化硅吸附剂在去除水体污染中的应用也在本发明的保护范围之内。
其中，所述的水体污染包括微污染有机物和重金属离子；其中，所述的微污染有机物优选四环素、土霉素或苯酚，所述的重金属离子优选Cu或Ni。
有益效果：
与现有技术相比，本发明具有如下优势：
(1)本发明公开了一种一步式制备磁性介孔氧化硅的方法，缩短了制备流程，并且利用共沉淀法制备出的磁性介孔氧化硅具有较高的磁性，在使用过程中便于用磁铁进行快速分离。
(2)本发明所制备的磁性介孔氧化硅既可以通过模板剂(CTAB)的疏水段吸附分子态的微污染有机物，又可以通过胺基试剂提供的位点吸附溶液中的重金属离子，可以同时高效净化复合污染水体。
附图说明
图1为本发明实施例1中磁性介孔氧化硅的透射电镜图片；
图2为本发明实施例1中磁性介孔氧化硅的氮气吸附/脱附等温线；
图3为本发明实施例1中磁性介孔氧化硅的磁滞回线。
具体实施方式
实施例1
将8.6g的四水合氯化亚铁和23.5g六水合三氯化铁溶于500mL去氧离子水中，然后转移入1000mL三口烧瓶中。分别向混合溶液中滴加6g油酸，并加入8g氢氧化钠以及2.5gCTAB，将温度升至80℃，反应30min，利用外加磁铁分离得到磁性粒子。将步骤所制得的磁性粒子加入含有25g CTAB的碱性溶液中，并加入50g正硅酸乙酯和10gγ-氨丙基三乙氧基硅烷，搅拌至完全混合，升温至80℃，水热反应2h，收集反应生成的固体产物，清洗后于60℃下烘干。制得磁性介孔氧化硅。然后取0.01g磁性介孔氧化硅，加入到100mL有机物与重金属的混合溶液中，混合溶液的初始浓度分别为：有机物(四环素、土霉素和苯酚)：100mg/L，重金属(Cu和Ni)：1mmol/L。在25℃下吸附至平衡后，测定剩余浓度。吸附量分别为：四环素52.5mg/g，土霉素47.8mg/g，苯酚63.7mg/g，Cu 21.5mg/g，Ni 27.5mg/g。
实施例2
将12.9g的四水合氯化亚铁和32.25g六水合三氯化铁溶于500mL去氧离子水中，然后转移入1000mL三口烧瓶中。分别向混合溶液中滴加18g油酸，并加入24g氢氧化钠以及30gCTAB，将温度升至80℃，反应30min，利用外加磁铁分离得到磁性粒子。将步骤所制得的磁性粒子加入含有7.5g CTAB的碱性溶液中，并加入27g正硅酸乙酯和9gγ-氨丙基三乙氧基硅烷，搅拌至完全混合，升温至80℃，水热反应8h，收集反应生成的固体产物，清洗后于60℃下烘干。制得磁性介孔氧化硅。然后取0.01g磁性介孔氧化硅，加入到100mL有机物与重金属的混合溶液中，混合溶液的初始浓度分别为：有机物(四环素、土霉素和苯酚)：100mg/L，重金属(Cu和Ni)：1mmol/L。在25℃下吸附至平衡后，测定剩余浓度。吸附量分别为：四环素58.7mg/g，土霉素66.5mg/g，苯酚53.2mg/g，Cu 41.6mg/g，Ni 35.9mg/g。
实施例3
将4.3g的四水合氯化亚铁和11.75g六水合三氯化铁溶于500mL去氧离子水中，然后转移入1000mL三口烧瓶中。分别向混合溶液中滴加12g油酸，并加入10g氢氧化钠以及5gCTAB，将温度升至80℃，反应30min，利用外加磁铁分离得到磁性粒子。将步骤所制得的磁性粒子加入含有15g CTAB的碱性溶液中，并加入20g正硅酸乙酯和15gγ-氨丙基三乙氧基硅烷，搅拌至完全混合，升温至80℃，水热反应6h，收集反应生成的固体产物，清洗后于60℃下烘干。制得磁性介孔氧化硅。然后取0.01g磁性介孔氧化硅，加入到100mL有机物与重金属的混合溶液中，混合溶液的初始浓度分别为：有机物(四环素、土霉素和苯酚)：100mg/L，重金属(Cu和Ni)：1mmol/L。在25℃下吸附至平衡后，测定剩余浓度。吸附量分别为：四环素35.6mg/g，土霉素38.4mg/g，苯酚63.4mg/g，Cu 33.6mg/g，Ni 27.9mg/g。
实施例4
将2.5g的四水合氯化亚铁和5.8g六水合三氯化铁溶于500mL去氧离子水中，然后转移入1000mL三口烧瓶中。分别向混合溶液中滴加5.5g油酸，并加入9g氢氧化钠以及13gCTAB，将温度升至80℃，反应30min，利用外加磁铁分离得到磁性粒子。将步骤所制得的磁性粒子加入含有15g CTAB的碱性溶液中，并加入15g正硅酸乙酯和5gγ-氨丙基三乙氧基硅烷，搅拌至完全混合，升温至80℃，水热反应5h，收集反应生成的固体产物，清洗后于60℃下烘干。制得磁性介孔氧化硅。然后取0.01g磁性介孔氧化硅，加入到100mL有机物与重金属的混合溶液中，混合溶液的初始浓度分别为：有机物(四环素、土霉素和苯酚)：100mg/L，重金属(Cu和Ni)：1mmol/L。在25℃下吸附至平衡后，测定剩余浓度。吸附量分别为：四环素63.6mg/g，土霉素42.3mg/g，苯酚44.3mg/g，Cu 26.5mg/g，Ni 45.7mg/g。
Claims (10)
1.一种磁性介孔氧化硅吸附剂的制备方法，其特征在于，它包括如下步骤：
(1)向铁盐溶液中滴加油酸和含CTAB的碱性溶液，60～80℃下反应30～120min；
(2)利用外加磁铁分离步骤(1)中所得混合体系，得到的磁性粒子和液体部分，将磁性粒子与含CTAB的碱性溶液、硅源前驱体、胺基试剂混合，搅拌完全后升温至60～80℃反应2～8h，收集反应所得固体产物，清洗后烘干，即得。
2.根据权利要求1所述的制备方法，其特征在于，步骤(1)和(2)中，所述的碱性溶液为氨水或者氢氧化钠的水溶液。
3.根据权利要求1所述的制备方法，其特征在于，步骤(1)中，所述的铁盐溶液中包括二价铁盐和三价铁盐；其中，所述的二价铁盐为氯化亚铁、硫酸亚铁或硝酸亚铁，三价铁盐为氯化铁、硫酸铁或硝酸铁。
4.根据权利要求3所述的制备方法，其特征在于，步骤(1)中，二价铁盐、三价铁盐、油酸、碱性溶液中碱和CTAB的摩尔比为1：2～4：0.5～2：4～16：0.1～1。
5.根据权利要求1所述的制备方法，其特征在于，步骤(2)中，所述的硅源前驱体为正硅酸乙酯或正硅酸甲酯，所述的胺基试剂为γ―氨丙基三乙氧基硅烷和/或γ-氨丙基三甲氧基硅烷。
6.根据权利要求1所述的制备方法，其特征在于，步骤(2)中，CTAB、碱性溶液中碱、硅源前驱体和胺基试剂的摩尔比为1：1.5～3：5～9：1～3。
7.根据权利要求1所述的制备方法，其特征在于，步骤(2)中，磁性粒子的质量为步骤(2)中含CTAB的碱性溶液、硅源前驱体和胺基试剂总质量的5～15％。
8.权利要求1～7中任意一项制备得到的磁性介孔氧化硅吸附剂。
9.权利要求8所述的磁性介孔氧化硅吸附剂在去除水体污染中的应用。
10.根据权利要求9所述的应用，其特征在于，所述的水体污染包括微污染有机物和/或重金属离子。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710158776.XA CN106861635A (zh) | 2017-03-17 | 2017-03-17 | 磁性介孔氧化硅吸附剂及制备方法与其在去除水体中有机物和重金属复合污染中的应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710158776.XA CN106861635A (zh) | 2017-03-17 | 2017-03-17 | 磁性介孔氧化硅吸附剂及制备方法与其在去除水体中有机物和重金属复合污染中的应用 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106861635A true CN106861635A (zh) | 2017-06-20 |
Family
ID=59172582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710158776.XA Pending CN106861635A (zh) | 2017-03-17 | 2017-03-17 | 磁性介孔氧化硅吸附剂及制备方法与其在去除水体中有机物和重金属复合污染中的应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106861635A (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107626287A (zh) * | 2017-10-19 | 2018-01-26 | 上海纳米技术及应用国家工程研究中心有限公司 | 氨基化的纳米二氧化钛/二氧化硅复合纤维膜的制备方法及其产品和应用 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117606A (zh) * | 2006-03-28 | 2008-02-06 | 中国矿业大学 | 用于疏水磁性润滑轴承的疏水磁性润滑脂的制备 |
| CN104148021A (zh) * | 2014-07-31 | 2014-11-19 | 桂林理工大学 | 一种用于吸附水中重金属离子的双功能化介孔二氧化硅的制备方法 |
| CN104445214A (zh) * | 2014-11-03 | 2015-03-25 | 东华大学 | 一种介孔二氧化硅纳米空心球及其制备方法 |
| CN104475012A (zh) * | 2014-12-16 | 2015-04-01 | 湖北工业大学 | 一种Fe3O4@SiO2磁性纳米球及其制备方法和应用 |
| CN105084424A (zh) * | 2014-05-15 | 2015-11-25 | 吉林大学 | 一种核壳球状磁性介孔二氧化硅纳米复合材料的快速制备方法和应用 |
-
2017
- 2017-03-17 CN CN201710158776.XA patent/CN106861635A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101117606A (zh) * | 2006-03-28 | 2008-02-06 | 中国矿业大学 | 用于疏水磁性润滑轴承的疏水磁性润滑脂的制备 |
| CN105084424A (zh) * | 2014-05-15 | 2015-11-25 | 吉林大学 | 一种核壳球状磁性介孔二氧化硅纳米复合材料的快速制备方法和应用 |
| CN104148021A (zh) * | 2014-07-31 | 2014-11-19 | 桂林理工大学 | 一种用于吸附水中重金属离子的双功能化介孔二氧化硅的制备方法 |
| CN104445214A (zh) * | 2014-11-03 | 2015-03-25 | 东华大学 | 一种介孔二氧化硅纳米空心球及其制备方法 |
| CN104475012A (zh) * | 2014-12-16 | 2015-04-01 | 湖北工业大学 | 一种Fe3O4@SiO2磁性纳米球及其制备方法和应用 |
Non-Patent Citations (5)
| Title |
|---|
| CHEN YITU ET AL.: ""Synthesis and Pb2+ Removal Property of Amino-Functionalized Mesoporous Silica Synthesized by an Anionic surfactant Templating Route"", 《RARE METAL MATERIALS AND ENGINEERING》 * |
| JIAHONG WANG ET AL.: ""Tannic acid adsorption on amino-functionalized magnetic mesoporous silica"", 《CHEMICAL ENGINEERING JOURNAL》 * |
| R. DENOYEL ET AL.: ""Solubilization in Confined Surfactant Mesophases"", 《LANGMUIR》 * |
| 刘漫红等: "《纳米材料及其制备技术》", 31 August 2014, 冶金工业出版社 * |
| 朱增银等: ""介孔氧化硅在水污染防治中的应用研究进展"", 《水处理技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107626287A (zh) * | 2017-10-19 | 2018-01-26 | 上海纳米技术及应用国家工程研究中心有限公司 | 氨基化的纳米二氧化钛/二氧化硅复合纤维膜的制备方法及其产品和应用 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jia et al. | Adsorption removal and reuse of phosphate from wastewater using a novel adsorbent of lanthanum-modified platanus biochar | |
| Liu et al. | Magnetic zirconium-based metal–organic frameworks for selective phosphate adsorption from water | |
| Qiu et al. | Enhanced As (Ш) removal from aqueous solutions by recyclable Cu@ MNM composite membranes via synergistic oxidation and absorption | |
| CN103599751B (zh) | 巯基功能化磁性二氧化硅纳米材料的制备方法 | |
| CN105148852B (zh) | 一种巯基改性磁性MOFs吸附剂及其制备方法和应用 | |
| CN103301809B (zh) | 磁性载铁有序介孔碳及其制备方法和应用 | |
| Yu et al. | Synthesis of magnetic chrysotile nanotubes for adsorption of Pb (II), Cd (II) and Cr (III) ions from aqueous solution | |
| CN110732307B (zh) | 一种edta改性磁性纳米复合材料的制备方法及应用 | |
| CN103464091A (zh) | 一种改性膨润土负载纳米铁材料及其制备方法 | |
| CN107486132A (zh) | 一种纳米四氧化三铁多孔重金属吸附材料的制备方法 | |
| Li et al. | Thiol-functionalized metal–organic frameworks embedded with chelator-modified magnetite for high-efficiency and recyclable mercury removal in aqueous solutions | |
| CN107469765B (zh) | 一种硅藻土/铁酸镁复合材料的制备方法 | |
| CN107983295B (zh) | 核壳结构铁铜双金属材料及其制备方法和应用 | |
| CN105399176B (zh) | 一种磺酸基改性超顺磁纳米材料的制备方法及其应用 | |
| CN104971688B (zh) | 一种纳米磁性颗粒吸附剂的制备方法 | |
| CN110280209B (zh) | 一种水体磷吸附材料及其制备、应用方法 | |
| US20220306492A1 (en) | Efficient and Regenerable Nano Manganese Remover, and Preparation Method and Application Thereof | |
| Shan et al. | Magnetite/hydrated cerium (III) carbonate for efficient phosphate elimination from aqueous solutions and the mechanistic investigation | |
| CN108854938B (zh) | 氨基改性磁性CoFe2O4复合材料的制备方法及应用 | |
| CN105457599A (zh) | 一种磁性纳米吸附材料的合成及其用于处理重金属废液的方法 | |
| CN104001479A (zh) | 一种无机矿物水处理剂及其制备方法 | |
| CN105056890B (zh) | 一种磁性纳米盘以及利用其进行重金属污水处理的方法 | |
| CN104941573A (zh) | 载锰氧化物吸附剂及其制备方法和处理化学镀镍废液的应用 | |
| CN104289200B (zh) | 一种磁性hacc/氧化多壁碳纳米管吸附剂的制备方法及应用 | |
| CN106861635A (zh) | 磁性介孔氧化硅吸附剂及制备方法与其在去除水体中有机物和重金属复合污染中的应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170620 |