CN114160093A - Iron-amino functionalized mesoporous silica and preparation method and application thereof - Google Patents
Iron-amino functionalized mesoporous silica and preparation method and application thereof Download PDFInfo
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- CN114160093A CN114160093A CN202111449528.3A CN202111449528A CN114160093A CN 114160093 A CN114160093 A CN 114160093A CN 202111449528 A CN202111449528 A CN 202111449528A CN 114160093 A CN114160093 A CN 114160093A
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- mesoporous silica
- iron
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000005562 Glyphosate Substances 0.000 claims abstract description 39
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229940097068 glyphosate Drugs 0.000 claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 40
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 20
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000003463 adsorbent Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 9
- 239000000693 micelle Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- -1 iron ions Chemical group 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- B01J20/02—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
- B01J20/02—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
- B01J20/28—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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- 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
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F2101/306—Pesticides
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention relates to iron-amino functionalized mesoporous silica and a preparation method and application thereof, wherein the iron-amino functionalized mesoporous silica is obtained by sequentially carrying out amino modification and iron loading on mesoporous silica, and the specific surface area of the mesoporous silica is 150～600m2Per g, pore volume of 0.4-1.5 cm3(ii)/g, the average pore diameter is 5 to 30 nm. The iron-amino functionalized mesoporous silica provided by the invention has appropriate pore diameter and surface reactivity, has good adsorption effect on glyphosate in water, high adsorption rate and large adsorption quantity, and is low in raw material cost, simple and controllable in preparation steps, mild in reaction conditions, nontoxic in preparation process, green and environment-friendly, and expected to be industrially produced.
Description
Technical Field
The invention belongs to the technical field of treatment of water, wastewater, sewage or sludge, and particularly relates to iron-amino functionalized mesoporous silica, and a preparation method and application thereof.
Background
Glyphosate is a biocidal herbicide with the greatest yield and demand in the global market. Glyphosate has the advantage of being simple, effective, and economical compared to other herbicides, and is therefore widely used in agricultural and urban environments, resulting in a dramatic increase in the use of glyphosate herbicides. Excessive glyphosate easily enters natural water, and causes great harm to water environment and human health. Therefore, the problem of glyphosate treatment in water has become a major issue in the field of water treatment.
The method for treating the glyphosate wastewater mainly comprises the following steps: chemical oxidation, biological, chemical precipitation, membrane separation, adsorption, and the like. The adsorption method has been widely studied due to its convenient operation, low cost, high treatment efficiency and strong adaptability to pollutants. The glyphosate is adsorbed by the physical or chemical interaction of the surface of the adsorbent and the functional groups in the glyphosate molecule. The materials for adsorbing glyphosate at present mainly comprise active carbon, resin and the like.
The mesoporous silica material has the advantages of large specific surface area, easy surface modification, no environmental pollution and the like, and is a potential adsorbent material. But the silicon dioxide mesoporous material has low chemical activity and small ion exchange capacity, and the adsorption effect of the silicon dioxide mesoporous material applied to glyphosate is still not ideal.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides iron-amino functionalized mesoporous silica, a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the iron-amino functionalized mesoporous silica is obtained by sequentially carrying out amino modification and iron loading on mesoporous silica, and the specific surface area of the mesoporous silica is 150-600 m2Per g, pore volume of 0.4-1.5 cm3(ii)/g, the average pore diameter is 5 to 30 nm.
According to the scheme, the iron loading amount in the iron-amino functionalized mesoporous silica is 5-30 wt%.
The invention also comprises a preparation method of the iron-amino functionalized mesoporous silica, which comprises the following specific steps:
1) dissolving hydroxyethyl cellulose in water, heating, stirring and dissolving to obtain a hydroxyethyl cellulose aqueous solution, dissolving sodium metasilicate nonahydrate in water to obtain a sodium metasilicate nonahydrate solution, mixing the hydroxyethyl cellulose aqueous solution with the sodium metasilicate nonahydrate solution under the condition of heat preservation and stirring, adjusting the pH value of a system to 5-6 by using an acid, continuously heating and stirring for 2 hours, stopping heating, continuously stirring for 12-36 hours at normal temperature, aging for 20-30 hours at room temperature, centrifuging, washing, drying and roasting the solid obtained by centrifuging to obtain mesoporous silica;
2) adding the mesoporous silica obtained in the step 1) into an ethanol solution of 3-Aminopropyltrimethoxysilane (APTMS), stirring at room temperature for 20-30 h, washing with absolute ethanol, filtering, and drying to obtain amino functionalized silica;
3) the amino work obtained in the step 2)Adding FeCl into functionalized silicon dioxide3Stirring for 2-6 h, filtering, washing with isopropanol, and drying to obtain the product Fe-amino functionalized silicon dioxide.
According to the scheme, the viscosity of the hydroxyethyl cellulose in the step 1) is 250-6400 mPa & s, the mass concentration of the hydroxyethyl cellulose aqueous solution is 0.4-1.4% at 25 ℃.
According to the scheme, the concentration of the sodium metasilicate nonahydrate solution in the step 1) is 0.5-1.2 mol/L.
According to the scheme, the mass ratio of the hydroxyethyl cellulose in the hydroxyethyl cellulose aqueous solution in the step 1) to the sodium metasilicate nonahydrate in the sodium metasilicate nonahydrate solution is 1: 2-6.
According to the scheme, the hydrolysis condensation reaction conditions of the sodium metasilicate in the step 1) are as follows: reacting for 2-3 h at 80-140 ℃.
According to the scheme, the roasting process conditions in the step 1) are as follows: heating to 500-600 ℃ at room temperature at a heating rate of 1-5 ℃/min, and roasting for 3-6 h.
According to the scheme, the mass ratio of the 3-aminopropyltrimethoxysilane to the ethanol in the ethanol solution of the 3-aminopropyltrimethoxysilane in the step 2) is 0.01-0.2: 1.
according to the scheme, the mass ratio of the mesoporous silica in the step 2) to the 3-aminopropyltrimethoxysilane is 1: 0.1 to 1.8.
According to the scheme, the FeCl is obtained in the step 3)3The concentration of the isopropanol solution is 0.01-0.05 g/mL.
According to the scheme, the amino functionalized silicon dioxide and FeCl in the step 3)3In isopropanol solution of FeCl3The mass ratio of (1): 0.1 to 1.7.
The invention also comprises the application of the iron-amino functionalized mesoporous silica as an adsorbent in the aspect of removing glyphosate in water, and the specific use method comprises the following steps: adding the iron-amino functionalized mesoporous silica into a water body containing glyphosate, wherein the adding amount of the iron-amino functionalized mesoporous silica is 0.2-2 g/L, the pH value of a system is adjusted to 2-7, and stirring for 5-300 min.
The invention adopts hydroxyethyl cellulose asThe template and hydroxyethyl cellulose are aggregated to form micelles, the micelles are aggregated to form micelles, the outer surfaces of the micelles consist of hydrophilic groups of the surfactant, and the micelles are further aggregated to finally form a liquid crystal structure. Hydrolysis of sodium metasilicate nonahydrate under acidic conditions H+Can promote its formation into orthosilicic acid (H)4SiO4). Loading hydrolyzed precursor of sodium metasilicate nonahydrate, ortho silicic acid (H) by utilizing internal cavity and terminal hydrophilic group of template molecule hydroxyethyl cellulose4SiO4) The mesoporous silicon dioxide modified by 3-aminopropyl trimethoxy silane has a molecular structure containing one amino group and three silicon hydroxyl groups, is easy to perform condensation reaction with free silicon hydroxyl groups (-OH) on the surface of the mesoporous silicon dioxide, and is grafted to the mesoporous silicon dioxide. Introducing a Fe metal active component by utilizing the coordination of amino groups in the 3-aminopropyltrimethoxysilane and metal ions to obtain the Fe-AP-HMS organic-inorganic composite material (the content of the 3-aminopropyltrimethoxysilane is 1-20 wt%, and the loading capacity of iron is 5-30 wt%). The iron ions and P-O bonds in the glyphosate generate coordination action to adsorb the iron ions on the surface of the adsorbent, so that the glyphosate in the water body can be removed.
The invention has the beneficial effects that: 1. the iron-amino functionalized mesoporous silica provided by the invention has proper pore diameter and surface reactivity, and has good adsorption effect on glyphosate in water, high adsorption rate and large adsorption capacity.
2. The preparation method disclosed by the invention is low in raw material cost, simple and controllable in steps, mild in reaction conditions, non-toxic in preparation process, green and environment-friendly, and is expected to realize industrial production.
Drawings
Fig. 1 is a nitrogen adsorption and desorption isotherm and a pore size distribution diagram of the iron-amino functionalized mesoporous silica prepared in example 1 of the present invention;
FIG. 2 is a graph showing the equilibrium adsorption of the Fe-amino functionalized mesoporous silica prepared in example 1 at 25 ℃ to glyphosate solutions with different pH values;
FIG. 3 is a graph showing the equilibrium adsorption of the Fe-amino functionalized mesoporous silica prepared in example 1 at 25 ℃ to glyphosate solutions of different initial concentrations;
FIG. 4 is an EDS-mapping characterization chart of iron-amino functionalized mesoporous silica (Fe-AP-HMS) prepared in example 1.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention is further described in detail below with reference to the accompanying drawings.
Example 1
An iron-amino functionalized mesoporous silica is prepared by the following steps:
1) dissolving 12g of hydroxyethyl cellulose (HEC, viscosity of 250-400 mPas in 1% aqueous solution) in 1000mL of water, heating to 100 deg.C, stirring to dissolve to obtain hydroxyethyl cellulose aqueous solution, and mixing 56.84g of Na2SiO3·9H2Dissolving 350mL of deionized water in O to obtain a sodium metasilicate nonahydrate solution, then dropwise adding the sodium metasilicate nonahydrate solution into a hydroxyethyl cellulose solution under the stirring condition, regulating the pH value of the obtained mixed solution to 5-6 by using 2mol/L hydrochloric acid solution, reacting for 2 hours at 100 ℃, stopping heating, continuously stirring for 24 hours, then aging for 24 hours at room temperature, centrifuging, washing, drying at 105 ℃, grinding the obtained sample into powder, heating to 550 ℃ at the room temperature at the heating rate of 2 ℃/min in an air atmosphere, roasting for 6 hours, and removing a template to obtain a mesoporous silica material;
2) adding 0.81g of 3-aminopropyltrimethoxysilane (with the purity of 97 wt%) into 15.8g of absolute ethyl alcohol to prepare 3-aminopropyltrimethoxysilane solution, weighing 0.5g of the prepared mesoporous silica material, adding the obtained mesoporous silica material into the prepared 3-aminopropyltrimethoxysilane solution, stirring for 24 hours at room temperature, washing with absolute ethyl alcohol, filtering and drying to obtain amino functionalized silica;
3) taking 3g FeCl3·6H2Dissolving O in 120mL of isopropanol to obtain FeCl31.96g of the amino-functionalized silica prepared above was taken and added to FeCl3Stirring for 3h, filtering, washing off unreacted iron ions with isopropanol, and drying at 80 deg.CAnd obtaining the product Fe-amino functionalized mesoporous silica which is marked as Fe-AP-HMS.
In the iron-amino functionalized mesoporous silica of this example, the content of 3-aminopropyltrimethoxysilane measured by thermogravimetry was 19.04 wt%, and the iron loading capacity measured by plasma emission spectrometer (ICP) of PE company, usa was 10.29 wt%.
FIG. 1 is a nitrogen adsorption and desorption isotherm and a pore size distribution diagram of the iron-amino functionalized mesoporous silica prepared in this example, and it can be seen that the specific surface area of the iron-amino functionalized mesoporous silica prepared in this example is 202.76m2Per g, pore volume 0.49cm3The average pore diameter is 8.51nm, and the mesoporous material has good characteristics.
Taking a plurality of glyphosate solutions with the concentration of 100mg/L, adjusting the pH value to 2-9 respectively with 50mL of each glyphosate solution, adding 0.05g of the iron-amino functionalized mesoporous silica adsorbent prepared in the embodiment into each glyphosate solution, adsorbing for 180min at the temperature of 25 ℃, and testing the adsorption effect of the iron-amino functionalized mesoporous silica on glyphosate, wherein fig. 2 is a graph showing the equilibrium adsorption of the iron-amino functionalized mesoporous silica prepared in the embodiment on glyphosate solutions with different pH values at the temperature of 25 ℃, and as a result, it is found that when the pH value of the solution is between 2.0 and 3.0, the adsorption amount of the adsorbent on glyphosate tends to increase, and when the pH value is between 3.0 and 6.0, the adsorption amount of the adsorbent on glyphosate keeps higher, but when the pH value of the solution is more than 6.0, the adsorption amount drops sharply. At pH 4, 60.93mg/g was achieved.
Taking a plurality of glyphosate solutions with different concentrations of 25-200mg/L, adjusting the pH value to 3, adding 0.05g of the iron-amino functionalized mesoporous silica adsorbent prepared in the embodiment into each glyphosate solution, adsorbing the solution at 25 ℃ for 180min, and testing the adsorption effect of the iron-amino functionalized mesoporous silica on the glyphosate solutions with different concentrations, wherein fig. 3 is a graph of equilibrium adsorption of the iron-amino functionalized mesoporous silica prepared in the embodiment on the glyphosate solutions with different initial concentrations at 25 ℃, and it can be seen that when the initial concentration of the glyphosate solution is lower than 100mg/L, the glyphosate solutions and glyphosate on the surfaces of the adsorbent increase along with the increase of the concentrationThe phosphine concentration gradient is increased, so that the mass transfer driving force is increased, and the equilibrium adsorption capacity is gradually increased. When the initial concentration of the glyphosate is more than 100mg/L, the equilibrium adsorption quantity does not change greatly along with the increase of the concentration, because when the initial concentration of the glyphosate is more than 100mg/L, adsorption active sites are gradually filled with the glyphosate, and the adsorption reaches a saturated state. At C0The highest adsorption amount is achieved when the concentration is 200mg/L, and 65.84mg/g is achieved.
Taking three parts of 100mg/L glyphosate solution, 50mL each, adjusting the pH value of the glyphosate solution to 3, respectively adding 0.05g of the mesoporous silica material prepared in the step 1), the amino functionalized silica prepared in the step 2) and the final product of the iron-amino functionalized mesoporous silica into each part, adsorbing for 180min at the temperature of 25 ℃, and measuring the adsorption capacity of the mesoporous silica material to be 1.28mg/g, the adsorption capacity of the amino functionalized silica to be 30.72mg/g and the adsorption capacity of the iron-amino functionalized mesoporous silica to be 59.01 mg/g.
FIG. 4 is an EDS-mapping chart of the Fe-amino functionalized mesoporous silica (Fe-AP-HMS) prepared in this example, and it can be seen that Fe and N elements in the Fe-AP-HMS material are uniformly dispersed in the detected region, which indicates that APTMS and Fe are successfully loaded on the surface of HMS.
Claims (10)
1. The iron-amino functionalized mesoporous silica is characterized by being prepared by sequentially carrying out amino modification and iron loading on mesoporous silica, and the specific surface area of the mesoporous silica is 150-600 m2Per g, pore volume of 0.4-1.5 cm3(ii)/g, the average pore diameter is 5 to 30 nm.
2. The iron-amino functionalized mesoporous silica according to claim 1, wherein the loading amount of iron in the iron-amino functionalized mesoporous silica is 5-30 wt%.
3. The preparation method of the iron-amino functionalized mesoporous silica according to claim 1 or 2, which is characterized by comprising the following specific steps:
1) dissolving hydroxyethyl cellulose in water, heating, stirring and dissolving to obtain a hydroxyethyl cellulose aqueous solution, dissolving sodium metasilicate nonahydrate in water to obtain a sodium metasilicate nonahydrate solution, mixing the hydroxyethyl cellulose aqueous solution with the sodium metasilicate nonahydrate solution under the condition of heat preservation and stirring, adjusting the pH value of a system to 5-6 by using an acid, continuously heating and stirring for 2 hours, stopping heating, continuously stirring for 12-36 hours at normal temperature, aging for 20-30 hours at room temperature, centrifuging, washing, drying and roasting the solid obtained by centrifuging to obtain mesoporous silica;
2) adding the mesoporous silica obtained in the step 1) into an ethanol solution of 3-aminopropyltrimethoxysilane, stirring at room temperature for 20-30 h, washing with absolute ethanol, filtering, and drying to obtain amino functionalized silica;
3) adding the amino functionalized silicon dioxide obtained in the step 2) into FeCl3Stirring for 2-6 h, filtering, washing with isopropanol, and drying to obtain the product Fe-amino functionalized silicon dioxide.
4. The method for preparing the iron-amino functionalized mesoporous silica according to claim 3, wherein the hydroxyethyl cellulose in the step 1) has a viscosity of 250-6400 mPa-s at 25 ℃ and a mass concentration of 0.4-1.4% in the aqueous solution of the hydroxyethyl cellulose.
5. The method for preparing the iron-amino functionalized mesoporous silica according to claim 3, wherein the concentration of the sodium metasilicate nonahydrate solution in the step 1) is 0.5-1.2 mol/L; the mass ratio of the hydroxyethyl cellulose in the hydroxyethyl cellulose aqueous solution in the step 1) to the sodium metasilicate nonahydrate in the sodium metasilicate nonahydrate solution is 1: 2-6.
6. The method for preparing iron-amino functionalized mesoporous silica according to claim 3, wherein the hydrolysis and condensation reaction conditions of the sodium metasilicate in the step 1) are as follows: reacting for 2-3 h at 80-140 ℃.
7. The method for preparing the iron-amino functionalized mesoporous silica according to claim 3, wherein the roasting process conditions in the step 1) are as follows: heating to 500-600 ℃ at room temperature at a heating rate of 1-5 ℃/min, and roasting for 3-6 h.
8. The method for preparing the iron-amino functionalized mesoporous silica according to claim 3, wherein the mass ratio of the 3-aminopropyltrimethoxysilane to the ethanol in the ethanol solution of the 3-aminopropyltrimethoxysilane in the step 2) is 0.01-0.2: 1; the mass ratio of the mesoporous silica to the 3-aminopropyltrimethoxysilane in the step 2) is 1: 0.1 to 1.8.
9. The method for preparing Fe-amino functionalized mesoporous silica according to claim 3, wherein the FeCl in step 3) is3The concentration of the isopropanol solution is 0.01-0.05 g/mL; step 3) the amino-functionalized silica and FeCl3In isopropanol solution of FeCl3The mass ratio of (1): 0.1 to 1.7.
10. The application of the iron-amino functionalized mesoporous silica as an adsorbent in removing glyphosate in water is characterized in that the specific application method is as follows: adding the iron-amino functionalized mesoporous silica into a water body containing glyphosate, wherein the adding amount of the iron-amino functionalized mesoporous silica is 0.2-2 g/L, the pH value of a system is adjusted to 2-7, and stirring for 5-300 min.
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| CN109574021A (en) * | 2019-01-03 | 2019-04-05 | 武汉工程大学 | A method of Metaporous silicon dioxide material is prepared by template of hydroxyethyl cellulose |
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| CN109772280A (en) * | 2017-11-15 | 2019-05-21 | 浙江工商大学 | A method of for removing micro glyphosate in drinking water resource |
| CN109574021A (en) * | 2019-01-03 | 2019-04-05 | 武汉工程大学 | A method of Metaporous silicon dioxide material is prepared by template of hydroxyethyl cellulose |
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