CN114832784A - Phosphoric acid modified silicon dioxide microsphere and preparation method and application thereof - Google Patents
Phosphoric acid modified silicon dioxide microsphere and preparation method and application thereof Download PDFInfo
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- CN114832784A CN114832784A CN202210561038.0A CN202210561038A CN114832784A CN 114832784 A CN114832784 A CN 114832784A CN 202210561038 A CN202210561038 A CN 202210561038A CN 114832784 A CN114832784 A CN 114832784A
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- phosphoric acid
- silicon dioxide
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- 239000004005 microsphere Substances 0.000 title claims abstract description 62
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 59
- -1 Phosphoric acid modified silicon dioxide Chemical class 0.000 title claims abstract description 53
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000000463 material Substances 0.000 claims abstract description 47
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims abstract description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 235000012239 silicon dioxide Nutrition 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 22
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- 238000005406 washing Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000356 contaminant Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
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- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 150000005837 radical ions Chemical class 0.000 abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 abstract description 16
- 239000001301 oxygen Substances 0.000 abstract description 16
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
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- 229910004298 SiO 2 Inorganic materials 0.000 description 47
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- 238000011534 incubation Methods 0.000 description 5
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000013310 covalent-organic framework Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 150000004715 keto acids Chemical class 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000012552 review Methods 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
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- 125000000223 arsonoyl group Chemical group [H][As](*)(*)=O 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000383 hazardous chemical Substances 0.000 description 3
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- 239000011669 selenium Substances 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
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- 239000002121 nanofiber Substances 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000003 human carcinogen Toxicity 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
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- 210000003932 urinary bladder Anatomy 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- 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
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- 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
- B01J20/28014—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 form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a phosphoric acid modified silicon dioxide microsphere and a preparation method and application thereof. When the preparation method is used, firstly, 3-aminopropyl is introduced to the surface of the silica microsphere, and then phosphoric acid is grafted to the surface of the 3-aminopropyl functionalized silica microsphere to prepare the silica microsphere material with the surface modified with phosphoric acid. The material has simple preparation process and mild reaction condition, and is successfully applied to the removal of the oxygen-containing acid radical ion pollutants in the water body.
Description
Technical Field
The invention belongs to the field of water treatment, and particularly relates to a phosphoric acid modified silicon dioxide microsphere, a preparation method thereof and application thereof in water body oxygen-containing acid radical ion adsorption.
Background
Water pollution is a global major problem and poses serious health and environmental hazards. The U.S. Environmental protection agency considers some inorganic contaminants, particularly oxyanions, as contaminants that require preferential control over inorganic contaminants in water bodies (1. Keith et al, "ES & T Special reports: Priority pollutants: I-a periodic view, [ Environmental Science & Technology ] 1979,13, (4), 416-.
Industrial waste water contaminated with oxygen-containing acid ions, e.g. CrO 4 2- /Cr 2 O 7 2- And HAsO 4 2- /H 2 AsO 4 - /H 3 AsO 3 Seriously threatens human health and the natural environment. Arsenic, as a "class a" human carcinogen, can cause cancer (skin, liver, lung, bladder), cardiovascular and nervous system diseases, and immune problems.
Hexavalent chromium is a carcinogenic and mutagenic substance. In China, 5% of land contaminated by potentially toxic elements is chromium-contaminated land (document 3.Bailey et al "A review of potential Low-cost resources for heav metals"; Water Research 1999,33, (11),2469- 2 O 3 ) Polymer composition and core-shell nanofibers as point-of-use filtering tables for the metal sequencing ", Water Research 2019,148, 492-. In addition, some radioactive oxysalt ion contaminants (SeO) were also detected in the nuclear wastewater 3 2- /SeO 4 2- ) (document 6.Peak et al, "Mechanisms of selenium adsorption on oxides and hydroxides"Environmental Science and Technology 2002,36, (7), 1460-. Therefore, there is a pressing need to explore effective technologies for removing these pollutants from water bodies, thereby satisfying our needs for clean water. In the past decades, a number of techniques have been explored to remove these highly toxic, oxolate ions from water, including adsorption, biological treatment, chemical oxidation/reduction, Membrane filtration, etc. (Hu et al, "Efficient ionization of organic and inorganic polar substances by Biochar and Biochar-based materials", "Biochar" 2020,2, (11),47-64. Mishra et al, "rare sulfur oxide-based adsorbed PVDF-based nanoparticles for a colloidal inorganic removal of biological ions, and methods 2020,593,117422). For example, biological treatment has the problem of producing other secondary pollutants and large amounts of sludge (document 10.Narayani et al, "Chromium-Resistant Bacteria and the ir Environmental Condition for Hexavalent Chromium Removal: A Review," Environmental Science and Technology "2013, 43, (9), 955-1009.). Chemical oxidation/reduction produces more toxic substances. Membrane filtration is the adsorption of organic substances by the hydrophobic nature of the membrane, thus reducing the adsorption of heavy metal ions. In addition, the membrane needs to be replaced periodically, which is costly. Compared with other methods, the adsorption method has the advantages of simple operation, low energy consumption, recyclability and small secondary pollution, and is considered as the most promising application technology (document 11.Bolisetty et al, "stable technologies for water purification from metals: review and analysis", "Chemical Society Reviews" 2019,48, (2), 463. 487.). Several problems typically arise with conventional adsorbent materials: (I) the chemical and thermal stability is low; (II) low adsorption capacity; (III) the adsorption kinetics are relatively slow and the selectivity is relatively poor; (IV) poor recycling performance. Thus, the design and development stability is high and the selectivity is goodThe new adsorbent with large adsorption capacity is always a research hotspot in the field of removing the oxygen-containing acid radical ions.
Currently, researchers have designed and prepared different types of adsorption materials to remove metal oxyanion contaminants in wastewater, such as Metal Organic Framework (MOFs) materials, Covalent Organic Framework (COFs) materials, organic-inorganic hybrid materials, metal oxides, Molecularly Imprinted Polymers (MIPs), and Layered Double Hydroxide (LDHs) materials. (document 12.Lv et al, "Nanoscale zero value iron supported on MgAl-LDH-reduced produced graphene oxide: Enhanced performance in Cr (VI) removal, mechanism and regeneration", Journal of Hazardous Materials 2019,373, 176-. Cationized MOFs (metal organic frameworks) material synthesized by metal cations and nitrogen-containing ligands can selectively adsorb SeO in water body through anion exchange 4 2- 、HAsO 4 2- 、MnO 4 - And Cr 2 O 7 2- And oxolate ions (document 13.Sharma et al, "A water-stable ionic MOF for the selective capture of toxic oxo-acids of Se (VI) and As (V) and crystalline oxo-acids in the ion-exchange mechanism", (Angewandte chemical Edition 2020,132, (20), 7862. 7866. document 14.Kumar et al, "Fluorine-containing tri-carboxylic-synthesized silicate, and" (I) -base carboxylic acid-organic framework for separation of oxo-acids and removal of oxo-acids from water ", (I) -organic Chemistry 2021,60, (10), 7070). The cation COFs material can selectively remove HAsO in the water body through anion exchange and hydrogen bond action 4 2- ,SeO 4 2- 、Cr 2 O 7 2- 、CrO 4 2- 、ReO 4 - And MnO 4 - (document 15.Deng et al "Hydrolytically stable carbonaceous metal for rapid and effective removal of toxic oxygen-ions and gases from Water", Inorganic Chemistry Compounds 2019,58, (4),2899-l of toxic Cr(VI)oxoanions from water”,《Environmental Science&Technology 2018,53, (2), 878-. Although MOFs and COFs materials have adjustable pore channels and large specific surface areas and have certain application prospects in the aspect of removal of oxygen-containing acid radical ions, the synthesis cost is high and large-scale preparation is difficult. Metal oxides, while capable of interacting with a variety of oxolate ions, are relatively less selective. E.g. alpha-MnO 2 The nanofibers are capable of removing As (III) and As (V), although both As (III) and As (V) may be in the alpha-MnO 2 (100) Form a complex with the (110) surface, but the complex formed on the (100) surface is more stable (reference 18 Luo et al "sensing adsorption on. alpha. -MnO 2 nanoparticles and the signature of (100) facet as shared with (110), "Chemical Engineering Journal" 2018,331, 492-. MIPs have strong selectivity to target oxolate ions. The selectivity of MIPs depends on The spatial morphology of The MIPs material and The strength of The van der Waals and hydrogen bonding between The template oxyanion and The functional monomer, which is only good in adsorption performance of The template oxyanion and poor in broad spectrum in adsorption of The oxyanion (19. Fan et al "Development of an involved polymer for high and selective removal of The presented from water", "Science of The Total Environment" 2018,639, 110-.
In summary, the acting force between the adsorption sites and the oxygen-containing acid radical ions in the adsorbent, the stability, the broad spectrum and the cost of the adsorbent are important factors influencing the performance and the application of the adsorbent.
And the report that 3-aminopropyl is grafted on the surface of silicon dioxide and phosphoric acid is grafted on the surface of the silicon dioxide by utilizing the reaction of amino and phosphorus oxychloride to prepare the phosphoric acid modified silicon dioxide microspheres is not found for a while.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a phosphoric acid modified silicon dioxide microsphere, a preparation method and application thereof, which can be used for adsorbing and removing the pollutants containing the oxygen acid radical ions in the water body.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a phosphoric acid modified silica microsphere, which has the following structural schematic:
as a preferred technical scheme of the application, the phosphoric acid modified silica microspheres are prepared by grafting phosphoric acid on silica through a silanization reaction on the surface of a silica microsphere raw material and a nucleophilic substitution reaction of amino.
As a preferred technical scheme of the application, the used silica microsphere raw material can be purchased commercially or prepared by self.
Preferably, the particle size of the used silicon dioxide microsphere raw material is 5 mu m, the pore diameter is 10nm, and the specific surface area is 300m 2 /g。
In a second aspect, the invention also provides a preparation method of the phosphoric acid modified silica microsphere material, wherein after the surface of silica is modified with 3-aminopropyl, phosphorus oxychloride is added, and phosphoric acid is grafted on the surface of the silica microsphere through a nucleophilic substitution reaction of amino groups, so that the phosphoric acid modified silica microsphere is formed on the surface of the silica microsphere.
As a preferred technical scheme of the application, the preparation method of the phosphoric acid modified silica microspheres comprises the following specific steps:
(1) modifying the surface of the silica microsphere with a 3-aminopropyl functional group:
dispersing silica microspheres in an organic solvent, dropwise adding 3-aminopropyltrimethoxysilane, carrying out reflux reaction on the mixture for 16-72h, taking out the silica microspheres, washing the silica microspheres, and drying to obtain 3-aminopropyl modified silica microspheres; wherein the mass-to-volume ratio (m/v) of the silicon dioxide to the 3-aminopropyltrimethoxysilane is 5-10 g: 2-8 mL, preferably 5-10 g: 4 mL;
(2) preparation of phosphoric acid modified silica microspheres:
adding the dried 3-aminopropyl modified silica microspheres obtained in the step (1) into a reaction vessel, adding an organic solvent, preferably acetonitrile, into the reaction vessel, performing ultrasonic dispersion, adding an acid binding agent, slowly dropwise adding phosphorus oxychloride into the reaction vessel, reacting in an oil bath at the temperature of 40 +/-5 ℃ for 4 to 48 hours, preferably 24 hours, washing and drying the product to obtain phosphoric acid modified silica microspheres; wherein the mass-to-volume ratio (m/v) of the 3-aminopropyl modified silica microspheres to the phosphorus oxychloride is 1.0-5.0 g: 2-10 mL.
As a preferred technical scheme of the application, the organic solvent used in the step (1) is one or more of toluene, methanol, ethanol and isopropanol.
Preferably, the organic solvent is toluene or ethanol; more preferably toluene.
Wherein, when the reaction solvent is toluene, the reaction temperature is 110 +/-10 ℃.
When the reaction solvent is ethanol, the reaction temperature is 20-80 ℃, and preferably room temperature (20-25 ℃).
As a preferred embodiment of the present invention, in the step (1), when the silica microspheres are dispersed in the organic solvent by using an ultrasonic dispersion method.
In the present invention, in the step (1), the reaction is preferably followed by washing with absolute ethanol.
In the preferred embodiment of the present invention, in the step (1) and the step (2), the drying may be performed by a conventional drying method such as vacuum drying or freeze drying.
Preferably, when vacuum drying is adopted, the drying temperature is 40-80 ℃.
As a preferred technical scheme of the present application, in the step (2), the acid-binding agent is an organic base, specifically methylamine, dimethylamine, triethylamine, pyridine, or the like.
Preferably, the acid-binding agent is triethylamine.
The invention also discloses the phosphoric acid modified silicon dioxide microsphere prepared by the preparation method.
In a third aspect, the invention also protects the application of the phosphoric acid modified silica microspheres in removing the pollutants containing the oxygen acid radical ions in the water body.
Advantageous effects
Compared with the prior art, the phosphoric acid modified silicon dioxide microsphere and the preparation method and the application thereof provided by the invention have the following advantages:
1. the material of the invention has relatively wide applicable pH range, large saturated adsorption capacity to the oxygen-containing acid radical ions and Cr 2 O 7 2- ,AsO 4 3- ,SeO 4 2- The saturated adsorption capacity of the adsorbent is 84.15, 24.67 and 66.76mg/g respectively, and after the adsorbent is recycled for 4 times, the removal rate of the oxygen-containing acid radical ions can still reach over 86 percent;
2. the synthesis route of the invention has few steps, mild reaction conditions and high reaction efficiency, which is beneficial to the rapid and high-efficiency synthesis of the phosphoric acid modified silicon dioxide microspheres.
3. The preparation method of the phosphoric acid modified silicon dioxide microspheres is simple, the preparation cost is low, and large-scale production can be realized;
4. the modified silicon dioxide microsphere provided by the invention has excellent selectivity and NO 3 - And SO 4 2- To Cr in aqueous solution under the interference of 2 O 7 2- ,AsO 4 3- ,SeO 4 2- The removal rate of the catalyst is kept stable;
5. three oxygen atoms in tetrahedral phosphoric acid in the synthesized material can be fully coordinated with elements such as chromium, arsenic and selenium in tetrahedral or triangular pyramidal oxyacid radical ions continuously to form a stable octahedral configuration, thereby being beneficial to adsorbing the oxyacid radical ions.
Drawings
FIG. 1 is a schematic diagram of the preparation of phosphoric acid modified silica microspheres;
FIG. 2 shows 3mg SiO at different pH 2 @NH 2 @H 2 PO 3 For (a) 200. mu.g/L Cr in the aqueous solution 2 O 7 2- ,(b)1mg/L AsO 4 3- ,(c)200μg/L SeO 4 2- The removal efficiency of (2);
FIG. 3 is 3mg SiO 2 @NH 2 @H 2 PO 3 For Cr in aqueous solution 2 O 7 2- ,AsO 4 3- ,SeO 4 2- Saturated adsorption amount of (4);
FIG. 4 is 3mg SiO 2 @NH 2 @H 2 PO 3 For 200 mu g/L Cr in aqueous solution 2 O 7 2- ,AsO 4 3- ,SeO 4 2- The number of times of cyclic use of adsorption;
FIG. 5 is 3mg SiO 2 @NH 2 @H 2 PO 3 At 1mg/L NO 3 - And SO 4 2- To Cr in aqueous solution under the interference of 2 O 7 2- ,AsO 4 3- ,SeO 4 2- Selectivity of (2).
Detailed Description
The present invention will be described in further detail with reference to examples. The reagents or instruments used are not indicated by manufacturers, and are regarded as conventional products which can be purchased in the market.
EXAMPLE 1 preparation of phosphoric acid modified silica microsphere Material
1) Dispersing 6.2g of silicon dioxide microspheres in 70mL of anhydrous toluene under the action of ultrasound, dropwise adding 4mL of 3-aminopropyltrimethoxysilane, refluxing the final mixture in an oil bath at 103 ℃ for 24h, taking out the silicon dioxide microspheres, washing the silicon dioxide microspheres with anhydrous ethanol, and then placing the silicon dioxide microspheres in a vacuum drying oven at 80 ℃ for drying for 24h to obtain the 3-aminopropyl functionalized silicon dioxide microspheres (SiO) 2 @NH 2 )；
2) 2g of SiO are taken 2 @NH 2 Dispersing into 70mL of acetonitrile under the action of ultrasonic waves, adding 16mL of triethylamine, slowly dropwise adding 6mL of phosphorus oxychloride into the acetonitrile, reacting for 24h in an oil bath at 40 ℃, washing a product by using acetonitrile, water and absolute ethyl alcohol in sequence, and then drying for 24h in a vacuum drying oven at 80 ℃ to obtain phosphorusAcid modified silica microsphere materials (SiO) 2 @NH 2 @H 2 PO 3 )。
EXAMPLE 2 preparation of phosphoric acid modified silica microsphere Material
1) Dispersing 5g of silicon dioxide microspheres in 30mL of anhydrous toluene under the action of ultrasound, dropwise adding 4mL of 3-aminopropyltrimethoxysilane, refluxing the final mixture in an oil bath at 103 ℃ for 24h, taking out the silicon dioxide microspheres, washing the silicon dioxide microspheres with anhydrous ethanol, and then placing the silicon dioxide microspheres in a vacuum drying oven at 80 ℃ for drying for 24h to obtain the 3-aminopropyl functionalized silicon dioxide microspheres (SiO) 2 @NH 2 )；
2) Taking 1g of SiO 2 @NH 2 Dispersing the mixture into 30mL of acetonitrile under the action of ultrasonic waves, adding 16mL of triethylamine, slowly dropwise adding 6mL of phosphorus oxychloride into the mixture, reacting for 24h in an oil bath at 40 ℃, washing a product by using acetonitrile, water and absolute ethyl alcohol in sequence, and then drying for 24h in a vacuum drying oven at 80 ℃ to obtain the phosphoric acid modified silicon dioxide microsphere material (SiO) 2 @NH 2 @H 2 PO 3 )。
EXAMPLE 3 preparation of phosphoric acid modified silica microsphere Material
1) Dispersing 10g of silicon dioxide microspheres in 100mL of anhydrous toluene under the action of ultrasound, dropwise adding 4mL of 3-aminopropyltrimethoxysilane, refluxing the final mixture in an oil bath at 103 ℃ for 24h, taking out the silicon dioxide microspheres, washing the silicon dioxide microspheres with anhydrous ethanol, and then placing the silicon dioxide microspheres in a vacuum drying oven at 80 ℃ for drying for 24h to obtain the 3-aminopropyl functionalized silicon dioxide microspheres (SiO) 2 @NH 2 )；
2) 2g of SiO are taken 2 @NH 2 Dispersing the mixture into 50mL of acetonitrile under the action of ultrasonic waves, adding 16mL of triethylamine, slowly dropwise adding 6mL of phosphorus oxychloride into the mixture, reacting for 24h in an oil bath at 40 ℃, washing a product by using acetonitrile, water and absolute ethyl alcohol in sequence, and then drying for 24h in a vacuum drying oven at 80 ℃ to obtain the phosphoric acid modified silicon dioxide microsphere material (SiO) 2 @NH 2 @H 2 PO 3 )。
EXAMPLE 4 preparation of phosphoric acid modified silica microsphere Material
1) 6.2g of silica are takenDispersing the microspheres in 70mL of absolute ethanol under the action of ultrasound, dropwise adding 4mL of 3-aminopropyltrimethoxysilane, stirring the final mixture at room temperature for 72h, taking out the silica microspheres, washing the silica microspheres with absolute ethanol, and then drying the silica microspheres in a vacuum drying oven at 80 ℃ for 24h to obtain the 3-aminopropyl functionalized silica microspheres (SiO) 2 @NH 2 )；
2) 2g of SiO are taken 2 @NH 2 Dispersing the mixture into 70mL of acetonitrile under the action of ultrasonic waves, adding 16mL of triethylamine, slowly dropwise adding 6mL of phosphorus oxychloride into the mixture, reacting for 24h in an oil bath at 40 ℃, washing a product by using acetonitrile, water and absolute ethyl alcohol in sequence, and then drying for 24h in a vacuum drying oven at 80 ℃ to obtain the phosphoric acid modified silicon dioxide microsphere material (SiO) 2 @NH 2 @H 2 PO 3 )。
Product characterization
In potentiometric analysis (Table 1), SiO 2 Potential of-5.261.5 mV at SiO 2 @NH 2 The potential is changed to 27mV, which indicates that 3-aminopropyl trimethoxy silane is successfully grafted to the surface of the silicon dioxide microsphere; with SiO 2 @NH 2 In contrast, SiO 2 @NH 2 @H 2 PO 3 The medium potential was again changed to-11.9 mV, indicating successful addition of phosphoric acid to SiO 2 @NH 2 The above.
TABLE 1 SiO 2 ,SiO 2 @NH 2 ,SiO 2 @NH 2 @H 2 PO 3 Measurement of potential of
Performance testing
1. Material pair Cr under different solution pH 2 O 7 2- ,AsO 4 3- And SeO 4 2- Removal efficiency of (2):
respectively preparing 200 mu g/L Cr 2 O 7 2- ,AsO 4 3- And SeO 4 2- The standard solution (2) is added into each of seven tubes, each tube is 40mL, and the pH of the solution in each tube is adjusted to be the pH of the solutionIs 2,3, 4,5, 6, 7 and 8. Then respectively weighing SiO 2 ,SiO 2 @NH 2 ,SiO 2 @NH 2 @H 2 PO 3 3mg of the material was placed in 10mL centrifuge tubes, respectively, and then 5mL of an oxoacid ion standard solution of the corresponding pH was added thereto. The sample was then incubated in a multi-tube vortex mixer with shaking at 2500rpm for 2 h. After the incubation was completed, the tube was placed in a centrifuge and centrifuged at 3000rpm for 3 min. The supernatant was filtered through a 0.22 μm aqueous filter head, and then 100. mu.L of concentrated nitric acid was added to the obtained filtrate, and after mixing, the concentration of the oxoacid ion was measured by ICP-OES. The pH experiment was repeated 3 times for each solution. Standard curve concentration of the oxygenate ion: 0,5, 10, 50, 100, 150 and 200 mu g/L Cr are respectively prepared 2 O 7 2- ,AsO 4 3- And SeO 4 2- Solutions, 5mL per tube, were adjusted to pH 2,3, 4,5, 6, 7, 8 for each group.
The results are shown in FIG. 2a, SiO 2 @NH 2 @H 2 PO 3 Materials for Cr in the pH range examined 2 O 7 2- The removal efficiency of the catalyst is better than that of SiO 2 And SiO 2 @NH 2 A material. In particular to Cr in a solution of pH 4 2 O 7 2- The removal efficiency of (2) is 100%, while SiO 2 And SiO 2 @NH 2 For Cr 2 O 7 2- The removal efficiency of (a) was 9.06% and 4.17%, respectively. In FIG. 2b, SiO 2 @NH 2 @H 2 PO 3 Materials except for AsO in solution at pH 2 4 3- Is less efficient than SiO 2 @NH 2 In addition, the material is specific to AsO in the remaining pH range 4 3- The removal rate of the catalyst is better than that of SiO 2 And SiO 2 @NH 2 . In particular to AsO in a solution at pH 4 4 3- The removal efficiency of (2) was 88%, while SiO 2 And SiO 2 @NH 2 To AsO 4 3- The removal efficiencies of (a) were 5.33% and 7.20%, respectively. In FIG. 2c, SiO 2 @NH 2 @H 2 PO 3 Materials other than at pH 2SeO 4 2- Removal efficiency and SiO 2 @NH 2 In addition to the same, at other pH ranges for SeO 4 2- The removal efficiency of the catalyst is better than that of SiO 2 And SiO 2 @NH 2 . In particular SiO in a solution at pH 3 2 @NH 2 @H 2 PO 3 For SeO 4 2- 77.30% and SiO 2 And SiO 2 @NH 2 For SeO 4 2- The removal efficiencies of (a) were 0 and 32.75%, respectively.
2.3 materials for Cr with different concentrations in water solution 2 O 7 2- ,AsO 4 3- ,SeO 4 2- Saturated adsorption amount of (2):
respectively preparing pH 4 and Cr 2 O 7 2- ,AsO 4 3- And SeO 4 2- The standard solution of (1) is 40mL in each tube, and the concentration of each tube is 5, 10, 25, 50, 75, 100 and 125 mg/L. Then respectively weighing 3mg of SiO 2 ,SiO 2 @NH 2 ,SiO 2 @NH 2 @H 2 PO 3 Placed in a 10mL centrifuge tube, and then 5mL of the corresponding concentration of the oxoacid ion solution was added thereto. The sample was then incubated in a multi-tube vortex mixer with shaking at 2500rpm for 2 h. After the incubation was completed, the tube was placed in a centrifuge and centrifuged at 3000rpm for 3 min. The supernatant was filtered through a 0.22 μm aqueous filter head, and then 100. mu.L of concentrated nitric acid was added to the obtained filtrate, and after mixing, the concentration of the oxoacid ion was measured by ICP-OES. The saturated adsorption capacity experiment of the material on the oxygen-containing acid radical ions is repeated for 3 times respectively. Standard curve concentration of the oxygenate ion: respectively preparing Cr with pH 4 and concentration of 0,1, 5, 10, 20, 50, 100 and 150mg/L 2 O 7 2- ,AsO 4 3- And SeO 4 2- The solutions were 5mL each.
The results are shown in FIG. 3, SiO 2 @NH 2 @H 2 PO 3 For Cr 2 O 7 2- 、AsO 4 3- And SeO 4 2- The saturated adsorption amounts of (A) are 84.15, 25.67 and 71.21mg/g respectively; and SiO 2 For Cr 2 O 7 2- 、AsO 4 3- And SeO 4 2- The saturated adsorption amounts of (A) are respectively 0, 3.04 and 11.11 mg/g; SiO 2 2 @NH 2 For Cr 2 O 7 2- 、AsO 4 3- And SeO 4 2- The saturated adsorption amounts of (A) were 15.58, 18.17 and 21.93mg/g, respectively. The results demonstrate that SiO 2 @NH 2 @H 2 PO 3 For Cr 2 O 7 2- 、AsO 4 3- And SeO 4 2- The saturated adsorption capacity of the catalyst is obviously superior to that of SiO 2 And SiO 2 @NH 2 。
3.3mg SiO 2 @NH 2 @H 2 PO 3 For 200 mu g/L Cr in aqueous solution 2 O 7 2- ,AsO 4 3- ,SeO 4 2- Number of adsorption cycles:
respectively preparing the Cr with the pH value of 4 and the concentration of 200 mu g/L 2 O 7 2- ,AsO 4 3- ,SeO 4 2- 40mL each of the standard solutions. Weighing 3mg SiO 2 @NH 2 @H 2 PO 3 The obtained solution was placed in a 10mL centrifuge tube, and 5mL of the prepared oxoacid group ion solution was added thereto. The mixed sample is placed in a multi-tube vortex mixer and incubated for 2h at 2500rpm with shaking. After the incubation was completed, the tube was placed in a centrifuge and centrifuged at 3000rpm for 3 min. The supernatant was filtered through a 0.22 μm aqueous filter head, and then 100. mu.L of concentrated nitric acid was added to the obtained filtrate, and after mixing, the concentration of the oxoacid ion was measured by ICP-OES. SiO adsorbed with oxoacid radical ion 2 @NH 2 @H 2 PO 3 And (3) washing for 3 times by using 0.5mM HCl solution to release the oxygen-containing acid radical ions adsorbed by the material, then washing for 3 times by using deionized water, then adding 5mL of the same type of oxygen-containing acid radical ion solution, repeating the operations of incubation, centrifugation, filtration and detection, and reflecting the result of the second adsorption of the material by the content of the oxygen-containing acid radical ions in the obtained filtrate. Repeating the above steps of releasing, incubating, centrifuging and detecting twice, and obtaining the results respectivelyRepresenting the third and fourth adsorption performance of the material on the same concentration of the oxoacid ion. Standard curve concentration of the oxygenate ion: respectively preparing the mixture with pH of 4 and concentrations of 0,5, 10, 50, 100, 150 and 200 mug/L Cr 2 O 7 2- ,AsO 4 3- And SeO 4 2- The solutions were 5mL each.
The results of recycling the material are shown in FIG. 4, which shows that SiO is present 2 @NH 2 @H 2 PO 3 After being recycled for 4 times, the Cr is treated 2 O 7 2- ,AsO 4 3- And SeO 4 2- The removal efficiency can still reach 77.13%, 93.85% and 84.02%.
4.3mg SiO 2 @NH 2 @H 2 PO 3 At 1mg/L NO 3 - And SO 4 2- To Cr in aqueous solution under the interference of 2 O 7 2- ,AsO 4 3- ,SeO 4 2- Selectivity of (a):
preparing 40mL of mixed solution of three types of oxygen acid radical ions with pH 4 and concentration of 1 mg/L: 1) NO 3 - 、SO 4 2- 、Cr 2 O 7 2- ，2)NO 3 - 、SO 4 2- 、AsO 4 3- ，3)NO 3 - 、SO 4 2- 、SeO 4 2- . Weighing 3mg SiO 2 ,SiO 2 @NH 2 ,SiO 2 @NH 2 @H 2 PO 3 Respectively placing the materials into 10mL centrifuge tubes, and then adding 10mL of the prepared oxygen acid radical ion solution into the centrifuge tubes filled with the materials. The resulting sample was incubated for 2h with shaking at 2500rpm in a multi-tube vortex mixer. After the incubation was completed, the tube was placed in a centrifuge and centrifuged at 3000rpm for 3 min. The supernatant was filtered through a 0.22 μm water filter head, and then 100 μ L of concentrated nitric acid was added to the resultant liquid, after which the oxoanion concentration was measured by ICP-OES. Standard curve concentration of the oxygenate ion: three kinds of mixed solutions, each having a pH of 4 and a concentration of 0, 10, 50, 100, 200, 500, 800, 1000 μ g/L, were prepared in a volume of 10mL each.
The results are shown in FIG. 5, at 1mg/L NO 3 - And SO 4 2- SiO under the interference of 2 @NH 2 @H 2 PO 3 For Cr in solution 2 O 7 2- ,AsO 4 3- And SeO 4 2- The removal effects of (A) and (B) are respectively 98.02%, 80.00% and 84.12%, and these results show that SiO is contained in the solution 2 @NH 2 @H 2 PO 3 In the removal of Cr 2 O 7 2- ,AsO 4 3- And SeO 4 2- The selectivity is higher.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept and the scope of the appended claims is intended to be protected.
Claims (10)
1. A phosphate modified silica microsphere has the following structural schematic:
2. the silica microspheres modified with phosphoric acid according to claim 1, wherein the silica microspheres are commercially available or prepared by itself; preferably, the particle size of the used silicon dioxide microsphere raw material is 5 μm, the pore diameter is 10nm, and the specific surface area is 300m 2 /g。
3. A preparation method of a phosphoric acid modified silicon dioxide microsphere material is characterized in that after 3-aminopropyl is modified on the surface of silicon dioxide, phosphorus oxychloride is added, phosphoric acid is grafted on the surface of the silicon dioxide microsphere through nucleophilic substitution reaction of amino, and the phosphoric acid modified silicon dioxide microsphere is formed on the surface of the silicon dioxide microsphere.
4. The preparation method of the silica microsphere material modified by phosphoric acid according to claim 3, which is characterized by comprising the following specific steps:
(1) modifying the surface of the silica microsphere with a 3-aminopropyl functional group:
dispersing silica microspheres in an organic solvent, dropwise adding 3-aminopropyltrimethoxysilane, carrying out reflux reaction on the mixture for 16-72h, taking out the silica microspheres, washing the silica microspheres, and drying to obtain 3-aminopropyl modified silica microspheres; wherein the mass-to-volume ratio (m/v) of the silicon dioxide to the 3-aminopropyltrimethoxysilane is 5-10 g: 2-8 mL, preferably 5-10 g: 4 mL;
(2) preparation of phosphoric acid modified silica microspheres:
adding the dried 3-aminopropyl modified silica microspheres obtained in the step (1) into a reaction vessel, adding an organic solvent, preferably acetonitrile, into the reaction vessel, performing ultrasonic dispersion, adding an acid binding agent, slowly dropwise adding phosphorus oxychloride into the reaction vessel, reacting in an oil bath at the temperature of 40 +/-5 ℃ for 4 to 48 hours, preferably 24 hours, washing and drying the product to obtain phosphoric acid modified silica microspheres; wherein the mass-to-volume ratio (m/v) of the 3-aminopropyl modified silica microspheres to the phosphorus oxychloride is 1.0-5.0 g: 2-10 mL.
5. The method for preparing a phosphoric acid modified silica microsphere material according to claim 4, wherein the organic solvent used in the step (1) is one or more of toluene, methanol, ethanol and isopropanol; preferably, the organic solvent is toluene or ethanol; more preferably toluene.
6. The method for preparing a phosphoric acid modified silica microsphere material according to claim 5, wherein when the reaction solvent is toluene, the reaction temperature is 110 ± 10 ℃; when the reaction solvent is ethanol, the reaction temperature is 20-80 ℃.
7. The method for preparing a phosphoric acid modified silica microsphere material according to any one of claims 4 to 6, wherein in the step (1), the silica microspheres are dispersed in the organic solvent by ultrasonic dispersion.
8. The method for preparing a silica microsphere material modified by phosphoric acid according to any one of claims 4 to 6, wherein in the step (2), the acid-binding agent is an organic base, specifically one or more of methylamine, dimethylamine, triethylamine and pyridine, preferably triethylamine.
9. The phosphoric acid modified silica microsphere material prepared by the method for preparing a phosphoric acid modified silica microsphere material according to any one of claims 4 to 8.
10. Use of the silica microspheres modified with phosphoric acid according to any one of claims 1-2 and claim 9 for removing contaminants containing oxo-acid ions from a body of water.
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