CN108031437B - Composite material for adsorbing organic pollutants as well as preparation method and application thereof - Google Patents

Composite material for adsorbing organic pollutants as well as preparation method and application thereof Download PDF

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CN108031437B
CN108031437B CN201711286774.5A CN201711286774A CN108031437B CN 108031437 B CN108031437 B CN 108031437B CN 201711286774 A CN201711286774 A CN 201711286774A CN 108031437 B CN108031437 B CN 108031437B
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composite material
sulfonyl fluoride
titanium dioxide
adsorbing
silane coupling
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CN108031437A (en
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路建美
徐庆锋
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Suzhou University
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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
    • B01J20/22—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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

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  • Organic Chemistry (AREA)
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Abstract

The invention discloses a composite material for adsorbing organic pollutants, and a preparation method and application thereof2Dropwise adding 2-chloroethyl sulfonyl chloride into the saturated aqueous solution, and reacting to obtain 2-chloroethyl sulfonyl fluoride; dropwise adding 2-chloroethyl sulfonyl fluoride into ice water, then adding MgO under stirring, and reacting to obtain vinyl sulfonyl fluoride; dispersing rutile titanium dioxide nano rods treated by a silane coupling agent in an organic solvent, then dropwise adding vinyl sulfonyl fluoride, and reacting to obtain the composite material for adsorbing organic pollutants. The titanium dioxide is synthesized and subjected to surface treatment, and the obtained composite material has an excellent dye treatment effect.

Description

Composite material for adsorbing organic pollutants as well as preparation method and application thereof
Technical Field
The invention belongs to the field of organic-inorganic hybrid conjugated materials, and particularly relates to a composite material for adsorbing organic pollutants, a preparation method thereof and application thereof in effectively removing dyes in water.
Background
With the development of scientific technology, the connection between dyes and human daily life is increasingly tight. At present, synthetic dyes are widely applied to industries such as food, printing and dyeing, cosmetics, medicines and the like. About 12% of the dyes used worldwide every year are lost in their manufacturing and handling processes, of which 20% enter the environment through waste water, causing water environmental pollution. Therefore, the dye causes serious pollution to the water body. These dyes are generally biologically toxic and carcinogenic and are relatively difficult to biodegrade completely in the environment. Therefore, finding an efficient and energy-saving method for rapidly adsorbing the dye wastewater has become a hot problem of environmental research. In the existing adsorbing materials, the research on titanium dioxide mainly focuses on inorganic aspects, and the absorption of titanium dioxide in a visible light area is enlarged, so that the photocatalytic performance is improved, but the research on the adsorption of organic matters is little; hollow silica spheres absorb most of the substances due to their large specific surface area, but cannot specifically adsorb which substance. Therefore, it is necessary to develop a new preparation method to develop a new adsorbent material to improve the organic pollutant treating ability.
Disclosure of Invention
The invention provides a composite material for adsorbing organic pollutants, a preparation method thereof and effective removal application thereof to dyes in water, in particular to an active cationic dye represented by methyl orange, wherein the preparation method adopts an organic-inorganic hybrid conjugation method, the inorganic material and the organic material are connected by a silane coupling agent, and the active cationic dye is adsorbed by combining strong electron-withdrawing groups of the organic material with the capture capacity of titanium dioxide, so that the composite material leaves the water and the purpose of removing the pollutants in the water is achieved.
The invention adopts the following technical scheme:
a preparation method of a composite material for adsorbing organic pollutants comprises the following steps:
(1) to KHF2Dropwise adding 2-chloroethyl sulfonyl chloride into the saturated aqueous solution, and reacting to obtain 2-chloroethyl sulfonyl fluoride;
(2) dropwise adding 2-chloroethyl sulfonyl fluoride into ice water, then adding MgO under stirring, and reacting to obtain vinyl sulfonyl fluoride;
(3) dispersing rutile titanium dioxide nano rods treated by a silane coupling agent in an organic solvent, then dropwise adding vinyl sulfonyl fluoride, and reacting to obtain the composite material for adsorbing organic pollutants.
The invention also discloses a vinyl sulfonyl fluoride and a preparation method thereof, and the preparation method comprises the following steps:
(1) to KHF2Dropwise adding 2-chloroethyl sulfonyl chloride into the saturated aqueous solution, and reacting to obtain 2-chloroethyl sulfonyl fluoride;
(2) dropwise adding 2-chloroethyl sulfonyl fluoride into ice water, then adding MgO under stirring, and reacting to obtain vinyl sulfonyl fluoride.
In the technical scheme, in the step (1), the reaction time is 4-10 hours; after the reaction is finished, the liquid is separated to obtain a light yellow oily liquid, and then water is removed, preferably anhydrous sodium sulfate is added to remove water, so that the product 2-chloroethyl sulfonyl fluoride is obtained.
In the technical scheme, in the step (2), the reaction time is 4-10 hours, and the reaction temperature is 0-25 ℃; after the reaction is finished, the liquid separation treatment is carried out to obtain a light yellow oily liquid, and then water is removed, preferably anhydrous sodium sulfate is added to remove water, so that the product of the vinyl sulfonyl fluoride is obtained.
In the technical scheme, in the step (3), the rutile titanium dioxide nano-rods, the silane coupling agent and the toluene are mixed; then carrying out reflux reaction in a nitrogen atmosphere, preferably carrying out reflux reaction for 6-20 hours to completely react, carrying out centrifugal treatment and ethanol washing on a product after the reaction is finished, and drying to obtain the rutile titanium dioxide nanorod treated by the silane coupling agent, wherein the rutile titanium dioxide nanorod is white powder; the silane coupling agent is 3-aminopropyl triethoxysilane, and the organic solvent is dichloromethane.
In the technical scheme, in the step (3), the reaction time is 4-10 hours; after the reaction is finished, the product is subjected to centrifugal treatment, ethanol washing and drying to obtain the composite material for adsorbing the organic pollutants.
In the technical scheme, the average grain diameter of the rutile titanium dioxide nano-rod is 25 nm; in the preferred method of the invention, TiCl is taken4Adding into water, stirring to adjust the temperature to 90 ℃, reacting for 2h at 160 ℃ for 12h to obtain rutile titanium dioxide nanorods; more surface hydroxyl groups can load more organic materials, and the problem of low loading rate of the existing titanium dioxide is solved.
In the technical scheme, the 2-chloroethanesulfonyl chloride and the KHF2The molar ratio of (1) to (2.4-3); the molar ratio of the 2-chloroethyl sulfonyl fluoride to the MgO is 1 (0.55-1); the mass ratio of the silane coupling agent to the rutile titanium dioxide nano-rods is (2-3): 1; the mass ratio of the vinyl sulfonyl fluoride to the rutile titanium dioxide nano-rod treated by the silane coupling agent is (0.2-2): 1.
The invention also discloses the application of the composite material for adsorbing organic pollutants or vinyl sulfonyl fluoride in preparing organic pollutant treating agents or water treating agents; or the application of the vinyl sulfonyl fluoride in preparing the titanium dioxide-based water treatment agent.
The invention can be embodied as follows:
firstly, KHF is taken as raw material2Dissolving in water to form KHF2Adding 2-chloroethyl sulfonyl chloride dropwise into the saturated solution, reacting for more than 4h, separating the solution to obtain a light yellow oily liquid, adding anhydrous sodium sulfate to remove water in the light yellow oily liquid, and obtaining a product 2-chloroethyl sulfonyl fluoride;
secondly, dropwise adding 2-chloroethyl sulfonyl fluoride into ice water, adding MgO while stirring, keeping the temperature below 25 ℃, reacting for more than 4 hours, separating liquid to obtain light yellow oily liquid, adding anhydrous sodium sulfate to remove water in the light yellow oily liquid to obtain a product of vinyl sulfonyl fluoride (ESF);
thirdly, taking TiCl4Adding into water while stirring, heating the mixed solution to 90 deg.C while stirring for 2 hr, transferring into high pressure reactor, reacting at 160 deg.C for 12 hr to obtain rutile TiO2A nanorod;
fourthly, carrying out reflux reaction on the rutile titanium dioxide nanorods and silane coupling agent 3-aminopropyl triethoxysilane (KH 550) in toluene for more than 6 hours in nitrogen atmosphere to ensure that the rutile titanium dioxide nanorods and the silane coupling agent react completely, centrifuging the product, washing the product with ethanol, and drying the product at 70 ℃ to obtain white powder;
dispersing the product obtained in the fourth step into dichloromethane, performing ultrasonic treatment, dropwise adding ESF into the reaction solution, reacting at normal temperature for more than 4h, centrifuging the product, washing with ethanol, and drying at 70 ℃ to obtain a powdery sample; thus obtaining the organic dye adsorbent.
The rutile titanium dioxide nano rod prepared by the limited method is modified by an organic-inorganic hybrid method for the first time to form a porous structure so as to improve the adsorption performance of the rutile titanium dioxide nano rod and can be used for adsorbing and removing organic pollutants, particularly cationic dyes; the invention adopts rutile titanium dioxide nano-rod with average grain diameter of 25nm, and increases TiO2The defect density in the crystal lattice increases the concentration of current carriers, increases the quantity of electrons and holes and has stronger trapping in TiO2The capacity of the solution components (water, oxygen, organics) of the surface; therefore, the titanium dioxide can be combined with strong electron-withdrawing groups of organic materials, the capture capability is improved, the active cationic dye is adsorbed, and the problems of stable commercial titanium dioxide, less surface hydroxyl and less loaded organic materials are solved.
Drawings
FIG. 1 shows rutile TiO of example II2Transmission electron microscope image of the nano-rod;
FIG. 2 shows rutile TiO of example II2X-ray polycrystalline diffraction patterns of nanorods;
FIG. 3 shows silane coupling agent treated rutile TiO of EXAMPLE III2An X-ray photoelectron spectrum of the nanorod;
FIG. 4 shows the composite material (TiO) adsorbing organic contaminants in example III2-ESF) X-ray photoelectron energy spectrum;
FIG. 5 shows silane coupling agent treated titanium dioxide (P25 and rutile TiO) of example III2Nanorods) with a composite that adsorbs organic contaminants;
FIG. 6 shows the composite materials P25-ESF and TiO for adsorbing organic pollutants in example six2Graph of the effect of ESF on methyl orange adsorption;
FIG. 7 shows the composite materials P25-ESF and TiO for adsorbing organic pollutants in example seven2Graph of the effect of ESF on methyl orange adsorption.
Detailed Description
Example one
Preparation of 2-chloroethanesulfonyl fluoride 5.23 g KHF were weighed out2Dissolving in deionized water, stirring to dissolve to form a saturated solution, stirring for one hour, adding 4.56 g of 2-chloroethyl sulfonyl chloride, stirring at normal temperature for reaction for 6 hours, separating liquid to obtain a light yellow liquid, adding anhydrous sodium sulfate to remove water in the light yellow liquid, and obtaining a product 2-chloroethyl sulfonyl fluoride;
preparing vinyl sulfonyl fluoride, namely adding 6.5 g of 2-chloroethyl sulfonyl fluoride into a proper amount of ice water, weighing 0.98 g of MgO, adding the MgO into the mixed solution in batches, reacting for 6h while paying attention to the temperature controlled to be about 25 ℃, separating liquid to obtain light yellow oily liquid, and adding anhydrous sodium sulfate to remove water in the liquid to obtain a product, namely vinyl sulfonyl fluoride (ESF).
Example two
Rutile TiO 22Preparing nano-rod by taking 5ml of TiCl4Adding into 20ml water under stirring, and stirring the mixed solutionHeating to 90 deg.C, transferring into high pressure reaction kettle after 2 hr, and reacting at 160 deg.C for 12 hr to obtain rutile TiO2And (4) nanorods. FIG. 1 shows the above rutile TiO2The transmission electron microscope image of the nano-rod, FIG. 2 is the above TiO2The X-ray polycrystalline diffraction pattern of the nano rod proves the successful synthesis of rutile phase TiO2And (4) nanorods.
EXAMPLE III
Preparation of silane coupling agent-treated titanium dioxide 0.155g of rutile TiO having an average particle size of 25nm was taken2Dispersing the nano rod in toluene, carrying out ultrasonic treatment for 5min, adding 0.31 g KH550, vacuumizing, carrying out reflux reaction for 8h under the nitrogen atmosphere, centrifuging the product, washing with ethanol for 4 times, and drying at 70 ℃ to obtain a white powdery sample which is rutile TiO treated by a silane coupling agent2A nanorod;
0.5g of rutile TiO treated with silane coupling agent was taken2Dispersing the nano-rod in ultra-dry dichloromethane, slowly dropwise adding 1g of ESF into the mixed solution, reacting at normal temperature for 4h, centrifuging the product, washing with ethanol for 4 times, and drying at 70 ℃ to obtain a white powder sample which is a composite material (TiO) for adsorbing organic pollutants2-ESF）。
The rutile TiO of the invention2The nanorods were replaced with commercial P25 titanium dioxide, and the treatment steps were the same, to obtain (P25-ESF), by comparison, highlighting the advantages of the present invention.
FIG. 3, FIG. 4, and FIG. 5 are TiO, respectively2KH550 and TiO2An X-ray photoelectron spectrum and an infrared spectrum of the ESF, indicating the amino group of the silane coupling agent and the-SO of the ESF2F is successfully loaded on TiO2On the material.
Example four
0.5g of rutile TiO treated with silane coupling agent was taken2Dispersing the nano-rods in ultra-dry dichloromethane, slowly dropwise adding 0.5g of ESF into the mixed solution, reacting at normal temperature for 4 hours, centrifuging the product, washing with ethanol for 4 times, and drying at 70 ℃ to obtain a white powder sample which is a composite material for adsorbing organic pollutants.
EXAMPLE five
0.5g of rutile TiO treated with silane coupling agent was taken2The nano-rods are dispersed in the super-nano-particlesAnd slowly dripping 0.1g of ESF into the mixed solution in dry dichloromethane, reacting for 4 hours at normal temperature, centrifuging the product, washing for 4 times by using ethanol, and drying at 70 ℃ to obtain a white powder sample which is a composite material for adsorbing organic pollutants.
EXAMPLE six
EXAMPLE three composite materials P25-ESF and TiO adsorbing organic contaminants2ESF (electron cyclotron resonance) adsorption experiment on methyl orange, 60mg of composite material for adsorbing organic pollutants is weighed as an adsorbent, the adsorbent is placed in 50ml of 10ppm methyl orange aqueous solution, the mixture is stirred for 20min in a dark place, the solution is taken every 5min, an ultraviolet-visible spectrophotometer is used for testing the absorbance of a water sample at the wavelength of 460nm, the adsorption result is shown in figure 6 by referring to a standard curve, wherein the TiO within 15min2The adsorption effect of ESF is the best.
EXAMPLE seven
EXAMPLE three composite materials P25-ESF and TiO adsorbing organic contaminants2ESF (electron cyclotron resonance) adsorption experiment on methyl orange, 60mg of composite material for adsorbing organic pollutants is weighed as an adsorbent, the adsorbent is placed in 50ml of 5ppm methyl orange aqueous solution, the mixture is stirred for 20min in a dark place, the solution is taken every 5min, an ultraviolet-visible spectrophotometer is used for testing the absorbance of a water sample at the wavelength of 460nm, the adsorption result is shown in figure 7 by referring to a standard curve, wherein TiO is shown within 15min2The adsorption effect of ESF is the best.

Claims (3)

1. A preparation method of a composite material for adsorbing organic pollutants comprises the following steps:
(1) to KHF2Dropwise adding 2-chloroethyl sulfonyl chloride into the saturated aqueous solution, and reacting to obtain 2-chloroethyl sulfonyl fluoride;
(2) dropwise adding 2-chloroethyl sulfonyl fluoride into ice water, then adding MgO under stirring, and reacting to obtain vinyl sulfonyl fluoride;
(3) dispersing rutile titanium dioxide nanorods treated by a silane coupling agent in an organic solvent, then dropwise adding vinyl sulfonyl fluoride, and reacting to obtain a composite material for adsorbing organic pollutants;
in the step (1), the reaction time is 4-10 hours; after the reaction is finished, carrying out liquid separation treatment to obtain a light yellow oily liquid, and then removing water to obtain a product 2-chloroethyl sulfonyl fluoride;
in the step (2), the reaction time is 4-10 hours, and the reaction temperature is 0-25 ℃; after the reaction is finished, carrying out liquid separation treatment to obtain a light yellow oily liquid, and then removing water to obtain a product of vinyl sulfonyl fluoride;
in the step (3), the rutile titanium dioxide nano-rods, the silane coupling agent and the toluene are mixed; then carrying out reflux reaction in a nitrogen atmosphere, and after the reaction is finished, carrying out centrifugal treatment, ethanol washing and drying on a product to obtain a rutile titanium dioxide nanorod treated by the silane coupling agent; the silane coupling agent is 3-aminopropyl triethoxysilane, and the organic solvent is dichloromethane; the reaction time for preparing the composite material for adsorbing the organic pollutants is 4-10 hours, and after the reaction is finished, the product is subjected to centrifugal treatment, ethanol washing and drying to obtain the composite material for adsorbing the organic pollutants; the preparation method of the rutile titanium dioxide nano rod comprises the following steps of taking TiCl4Adding into water, stirring to adjust the temperature to 90 ℃, reacting for 2h at 160 ℃ for 12h to obtain rutile titanium dioxide nanorods;
2-chloroethanesulfonyl chloride with KHF2The molar ratio of (A) to (2.4-3); the molar ratio of the 2-chloroethyl sulfonyl fluoride to the MgO is 1: 0.55-1; the mass ratio of the silane coupling agent to the rutile titanium dioxide nano-rods is (2-3) to 1; the mass ratio of the vinyl sulfonyl fluoride to the rutile titanium dioxide nano-rod treated by the silane coupling agent is (0.2-2) to 1.
2. The organic pollutant adsorbing composite material prepared by the method for preparing the organic pollutant adsorbing composite material according to claim 1.
3. Use of the composite material for adsorbing organic contaminants according to claim 2 for the preparation of an organic contaminant treatment agent or a water treatment agent.
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