CN107442064B - Preparation method of hydrophobic zirconium dioxide-silicon dioxide composite adsorption material - Google Patents

Preparation method of hydrophobic zirconium dioxide-silicon dioxide composite adsorption material Download PDF

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CN107442064B
CN107442064B CN201710669433.XA CN201710669433A CN107442064B CN 107442064 B CN107442064 B CN 107442064B CN 201710669433 A CN201710669433 A CN 201710669433A CN 107442064 B CN107442064 B CN 107442064B
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CN107442064A (en
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杨靖
贾德宝
李淋钰
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Xian Polytechnic 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
    • B01J20/02—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
    • 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
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • 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 discloses a preparation method of a hydrophobic zirconium dioxide-silicon dioxide composite adsorption material, which adopts dimethyl diethoxysilane to replace the prior methyl triethoxysilane to treat hydrophilic SiO2Carrying out methylation modification on the sol to obtain methylation modified SiO2Sol, and ZrO prepared subsequently2Sol and methylated modified SiO2Sol fusion, baking and calcining to obtain hydrophilic SiO2The sol is subjected to methylation modification, so that the removal rate and the adsorption capacity of the adsorption material to the dye are better improved, and the method has good practical value.

Description

Preparation method of hydrophobic zirconium dioxide-silicon dioxide composite adsorption material
Technical Field
The invention belongs to the technical field of sewage adsorption treatment, and particularly relates to a preparation method of a hydrophobic zirconium dioxide-silicon dioxide composite adsorption material.
Background
At present, with the rapid development of the textile industry and related industries, dyes have been widely used in the textile, plastic, cosmetic and paper industries. The dye wastewater is not treated or discharged after not reaching the standard, so that the environment is greatly harmed, the dye wastewater with extremely low concentration can change the color of water, the water enters the water environment and then has high water toxicity, low light transmittance and high organic matter load content, and the water can be directly or indirectly consumed by human beings and animals, so that the method has very important significance for treating the dye-containing wastewater.
The dye waste water is difficult to remove by the conventional method not only because the structure of the dye is more and more complicated, but also because the components of the dye waste water are very complicated and have poor biodegradability. The dye wastewater is generally removed by methods such as an electrocoagulation method, a membrane separation method, an electrochemical method, a biological oxidation method, an adsorption method and the like. The electrocoagulation method has good treatment effect on suspended matters in the dye wastewater, but has large dosage, high cost and heavy secondary pollution. The membrane separation method can effectively remove all types of dyes, but generates a large amount of waste sludge, thereby causing secondary pollution. The electrochemical method adds a small amount of chemical agents or does not need adding chemical agents, does not produce secondary pollution, is convenient to manage, but consumes a large amount of electric energy. Compared with the common chemical method, the biological oxidation method is more superior, the operation and the management are convenient, the treatment cost is low, but the treatment time is long, the treatment effect is not ideal, toxic or carcinogenic intermediate products are easily generated, and the biological oxidation method is difficult to operate because the high salt and the toxicity of the dye wastewater often have the inhibition effect on organisms.
Compared with the above wastewater treatment methods, the adsorption method has the advantages of low investment, low cost and good dye removal effect, wherein the hydrophilic ZrO2-SiO2The composite adsorbing material is superior to pure SiO2The good acid-base tolerance of the adsorbent is widely used, but the adsorbent has certain limits on the removal rate of sewage with low dye concentration and low adsorption capacity.
Disclosure of Invention
The invention aims to provide a preparation method of a hydrophobic zirconium dioxide-silicon dioxide composite adsorption material, which solves the problem of the existing hydrophilic ZrO2-SiO2The composite adsorbing material has the problems of low dye removing efficiency and small adsorption capacity.
The technical scheme adopted by the invention is that the preparation method of the hydrophobic zirconium dioxide-silicon dioxide composite adsorption material comprises the following steps:
step 1, preparing methylated modified SiO2Sol gel
Fully mixing tetraethoxysilane, dimethyl diethoxysilane and absolute ethyl alcohol into a homogeneous solution, putting the homogeneous solution into an ice-water mixture, adding water and HCl or HNO while stirring3Stirring and refluxing the mixture at the temperature of between 50 and 75 ℃ for 2 to 5 hours, and cooling to room temperature to obtain the methylated modified SiO2Dissolving the sol for later use;
step 2, preparation of ZrO2Sol gel
Adding a proper amount of oxalic acid solution into a zirconium nitrate pentahydrate solution dropwise, stirring quickly, heating to 50-70 ℃, mixing fully to form a uniform liquid phase, keeping the temperature, adding glycerol while stirring, stirring and refluxing for 2-4h, and cooling to normal temperature to obtain clear and transparent ZrO2Sol;
step 3, preparing hydrophobic ZrO2-SiO2Sol gel
Adding proper amount of the methylated modified SiO in the step 12Adding the ZrO obtained in the step 2 into the sol while stirring2Rapidly stirring the mixed solution of the sol and the absolute ethyl alcohol for 30-60min to obtain the hydrophobic ZrO2-SiO2Sol;
step 4, the hydrophobic ZrO prepared in the step 32-SiO2Placing the sol in a culture dish, drying and grinding the sol into powder in a vacuum drying oven, then placing the powder in a program-controlled high-temperature furnace, and roasting the powder at a certain temperature to obtain the hydrophobic ZrO2-SiO2And (3) compounding the adsorption material.
The present invention is also characterized in that,
HCl or HNO in step 13The concentration of (A) is 1.0-2.0 mol/L.
In step 1, tetraethoxysilane, dimethyl diethoxysilane, absolute ethyl alcohol, water, HCl or HNO3In a molar ratio of 1: 0.4-0.6: 7.7-15.0: 7.3-12.0: 0.086-0.120.
In the step 2, the concentration of the zirconium nitrate pentahydrate solution is 0.2-0.6mol/L, and the concentration of the oxalic acid solution is 0.05-0.2 mol/L.
In the step 2, the molar ratio of the zirconium nitrate pentahydrate solution to the oxalic acid solution is 4.0-5.0: 1.
in the step 2, the volume of the glycerol is 20-35% of the sum of the volumes of the zirconium nitrate pentahydrate solution and the oxalic acid solution.
ZrO in step 32Sol and methylated modified SiO2The mol ratio of the sol is 0.05-1.0: 1.
the drying temperature in the step 4 is 30-60 ℃.
The roasting parameters in the step 4 are as follows: heating to 350-450 deg.C at 1.0-5.0 deg.C/min in non-oxidizing gas atmosphere, calcining for 2-5h, and naturally cooling to room temperature.
The invention has the beneficial effects that: the preparation method of the hydrophobic zirconium dioxide-silicon dioxide composite adsorption material adopts dimethyldiethoxysilane to replace the prior methyltriethoxysilane to prepare hydrophilic SiO2Carrying out methylation modification on the sol to obtain methylation modified SiO2Sol, and ZrO prepared subsequently2Sol and methylated modified SiO2Sol fusion, baking and calcining to obtain hydrophilic SiO2The sol is subjected to methylation modification, so that the removal rate and the adsorption capacity of the adsorption material to the dye are better improved, and the method has good practical value.
Drawings
FIG. 1 is a view showing the preparation of hydrophobic ZrO according to the present invention2-SiO2Composite adsorbent material and hydrophilic ZrO2-SiO2The composite adsorption material is used for comparing the removal rates of rhodamine B, methylene blue and neutral red under the same conditions by a broken line;
FIG. 2 shows a hydrophobic ZrO prepared by the present invention2-SiO2Composite adsorbent material and hydrophilic ZrO2-SiO2And (3) carrying out column comparison on the adsorption capacity of the composite adsorption material to rhodamine B, methylene blue and neutral red under the same condition.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The preparation method of the hydrophobic zirconium dioxide-silicon dioxide composite adsorption material comprises the following steps:
step 1, preparing methylated modified SiO2Sol gel
Fully mixing tetraethoxysilane, dimethyl diethoxysilane and absolute ethyl alcohol into a homogeneous solution, putting the homogeneous solution into an ice-water mixture, adding water and HCl or HNO while stirring3Stirring and refluxing the mixture at the temperature of between 50 and 75 ℃ for 2 to 5 hours, and cooling to room temperature to obtain the methylated modified SiO2Dissolving the sol for later use; wherein, HCl or HNO3The concentration of the (A) is 1.0-2.0 mol/L; tetraethoxysilane, dimethyldiethoxysilane, absolute ethanol, water, HCl or HNO3In a molar ratio of 1:0.4-0.6：7.7-15.0：7.3-12.0：0.086-0.120；
step 2, preparation of ZrO2Sol gel
Dropwise adding oxalic acid solution with the concentration of 0.05-0.2mol/L into zirconium nitrate pentahydrate solution with the concentration of 0.2-0.6mol/L, quickly stirring and heating to 50-70 ℃, fully mixing to form uniform liquid phase, keeping the temperature, then adding glycerol while stirring, stirring and refluxing for 2-4h, and cooling to normal temperature to obtain clear and transparent ZrO2Sol; wherein the molar ratio of the zirconium nitrate pentahydrate solution to the oxalic acid solution is 4.0-5.0: 1; the volume of the glycerol is 20-35% of the sum of the volumes of the zirconium nitrate pentahydrate solution and the oxalic acid solution;
step 3, preparing hydrophobic ZrO2-SiO2Sol gel
Taking the molar ratio of 0.05-1.0:1 ZrO2Sol and methylated modified SiO2Sol, then methylating and modifying the SiO2Adding the ZrO obtained in the step 2 into the sol while stirring2Rapidly stirring the mixed solution of the sol and the absolute ethyl alcohol for 30-60min to obtain the hydrophobic ZrO2-SiO2Sol;
step 4, the hydrophobic ZrO prepared in the step 32-SiO2Placing the sol in a culture dish, drying and grinding the sol into powder at 30-60 ℃ in a vacuum drying oven, then placing the powder in a program-controlled high-temperature furnace, and roasting the powder at a certain temperature to obtain the hydrophobic ZrO2-SiO2The composite adsorbing material comprises the following roasting parameters: heating to 350-450 deg.C at 1.0-5.0 deg.C/min in non-oxidizing gas atmosphere, calcining for 2-5h, and naturally cooling to room temperature.
Example 1
(1) Fully mixing tetraethoxysilane, dimethyl diethoxysilane and absolute ethyl alcohol into a homogeneous solution, placing the homogeneous solution into an ice water mixture, adding a mixture of water and HCl with the concentration of 1.0mol/L while stirring, stirring and refluxing for 5 hours at the temperature of 50 ℃, and cooling to room temperature to obtain the methylated modified SiO2Sol; wherein the ethyl orthosilicate, the dimethyl diethoxysilane, the absolute ethyl alcohol, the water and the HNO3In a molar ratio of 1: 0.4: 7.7: 7.3: 0.086;
(2) the concentration was set to 0.Adding 05mol/L oxalic acid solution into 0.2mol/L zirconium nitrate pentahydrate solution dropwise until the molar ratio of the zirconium nitrate pentahydrate solution to the oxalic acid solution is 4.0: stopping dripping at 1 hour, rapidly stirring, heating to 50 deg.C, mixing to obtain uniform liquid phase, maintaining temperature, adding glycerol under stirring, stirring and refluxing for 4 hr, and cooling to room temperature to obtain clear and transparent ZrO2Sol; wherein the volume of the glycerol is 20 percent of the sum of the volumes of the zirconium nitrate pentahydrate solution and the oxalic acid solution;
(3) taking the molar ratio of 0.05: 1 ZrO2Sol and methylated modified SiO2Sol, then methylating and modifying the SiO2Adding ZrO while stirring the sol2Rapidly stirring the mixed solution of the sol and the absolute ethyl alcohol for 30min to obtain the hydrophobic ZrO2-SiO2Sol;
(4) hydrophobic ZrO2-SiO2Placing the sol in a culture dish, drying and grinding the sol into powder in a vacuum drying oven at 30 ℃, and then placing the powder in a program-controlled high-temperature furnace for roasting to obtain the hydrophobic ZrO2-SiO2The composite adsorbing material comprises the following roasting parameters: in N2Heating to 350 deg.C at 5.0 deg.C/min in atmosphere, calcining for 5 hr, and naturally cooling to room temperature.
Example 2
(1) Fully mixing tetraethoxysilane, dimethyl diethoxysilane and absolute ethyl alcohol into a homogeneous solution, placing the homogeneous solution into an ice water mixture, adding a mixture of water and HCl with the concentration of 1.5mol/L while stirring, stirring and refluxing for 3 hours at the temperature of 60 ℃, and cooling to room temperature to obtain the methylated modified SiO2Sol; wherein the ethyl orthosilicate, the dimethyl diethoxysilane, the absolute ethyl alcohol, the water and the HNO3In a molar ratio of 1: 0.5: 10.0: 9.0: 0.10;
(2) dropwise adding oxalic acid solution with the concentration of 0.15mol/L into zirconium nitrate pentahydrate solution with the concentration of 0.4mol/L until the molar ratio of the zirconium nitrate pentahydrate solution to the oxalic acid solution is 4.5: stopping dripping at 1 hour, rapidly stirring, heating to 60 deg.C, mixing to obtain uniform liquid phase, maintaining temperature, adding glycerol while stirring, stirring and refluxing for 3 hr, and cooling to room temperature to obtain clear and transparent ZrO2Sol; wherein the volume of the glycerol is 30 percent of the sum of the volumes of the zirconium nitrate pentahydrate solution and the oxalic acid solution;
(3) taking the molar ratio of 0.15: 1 ZrO2Sol and methylated modified SiO2Sol, then methylating and modifying the SiO2Adding ZrO while stirring the sol2Rapidly stirring the mixed solution of the sol and the absolute ethyl alcohol for 45min to obtain hydrophobic ZrO2-SiO2Sol;
(4) hydrophobic ZrO2-SiO2Placing the sol in a culture dish, drying and grinding the sol into powder at 40 ℃ in a vacuum drying oven, and then placing the powder in a program-controlled high-temperature furnace for roasting to obtain the hydrophobic ZrO2-SiO2The composite adsorbing material comprises the following roasting parameters: in N2Heating to 400 ℃ at the speed of 3.0 ℃/min in the atmosphere, roasting for 3h, and naturally cooling to room temperature.
Example 3
(1) Fully mixing tetraethoxysilane, dimethyl diethoxysilane and absolute ethyl alcohol into a homogeneous solution, placing the homogeneous solution into an ice-water mixture, adding water and HNO with the concentration of 2mol/L while stirring3Stirring and refluxing the mixture at the temperature of 75 ℃ for 2h, and cooling to room temperature to obtain the methylated modified SiO2Sol; wherein the molar ratio of ethyl orthosilicate, dimethyl diethoxysilane, absolute ethyl alcohol, water and HCl is 1: 0.6: 15.0: 12.0: 0.12;
(2) dropwise adding oxalic acid solution with the concentration of 0.2mol/L into zirconium nitrate pentahydrate solution with the concentration of 0.6mol/L until the molar ratio of the zirconium nitrate pentahydrate solution to the oxalic acid solution is 5: stopping dripping at 1 hour, rapidly stirring, heating to 70 deg.C, mixing to obtain uniform liquid phase, maintaining temperature, adding glycerol under stirring, stirring and refluxing for 2 hr, and cooling to room temperature to obtain clear and transparent ZrO2Sol; wherein the volume of the glycerol is 35 percent of the sum of the volumes of the zirconium nitrate pentahydrate solution and the oxalic acid solution;
(3) taking the molar ratio of 1.0:1 ZrO2Sol and methylated modified SiO2Sol, then methylating and modifying the SiO2Adding ZrO while stirring the sol2Quickly stirring the mixed solution of the sol and the absolute ethyl alcohol for 60min to obtain hydrophobic ZrO2-SiO2Sol;
(4) hydrophobic ZrO2-SiO2Placing the sol in a culture dish, drying and grinding the sol into powder at 50 ℃ in a vacuum drying oven, and then placing the powder in a program-controlled high-temperature furnace for roasting to obtain the hydrophobic ZrO2-SiO2The composite adsorbing material comprises the following roasting parameters: in N2Heating to 450 deg.C at 5.0 deg.C/min in atmosphere, calcining for 2 hr, and naturally cooling to room temperature.
Example 4
(1) Fully mixing tetraethoxysilane, dimethyl diethoxysilane and absolute ethyl alcohol into a homogeneous solution, putting the homogeneous solution into an ice water mixture, adding water and HNO with the concentration of 1.8mol/L while stirring3Stirring and refluxing the mixture at the temperature of 60 ℃ for 4 hours, and cooling to room temperature to obtain the methylated modified SiO2Sol; wherein the molar ratio of ethyl orthosilicate, dimethyl diethoxysilane, absolute ethyl alcohol, water and HCl is 1: 0.4: 8.0: 7.3: 0.086;
(2) dropwise adding oxalic acid solution with the concentration of 0.1mol/L into zirconium nitrate pentahydrate solution with the concentration of 0.3mol/L until the molar ratio of the zirconium nitrate pentahydrate solution to the oxalic acid solution is 4.5: stopping dripping at 1 hour, rapidly stirring, heating to 60 deg.C, mixing to obtain uniform liquid phase, maintaining temperature, adding glycerol under stirring, stirring and refluxing for 4 hr, and cooling to room temperature to obtain clear and transparent ZrO2Sol; wherein the volume of the glycerol is 20 percent of the sum of the volumes of the zirconium nitrate pentahydrate solution and the oxalic acid solution;
(3) taking the molar ratio of 0.15: 1 ZrO2Sol and methylated modified SiO2Sol, then methylating and modifying the SiO2Adding ZrO while stirring the sol2Rapidly stirring the mixed solution of the sol and the absolute ethyl alcohol for 60min to obtain hydrophobic ZrO2-SiO2Sol;
(4) hydrophobic ZrO2-SiO2Placing the sol in a culture dish, drying and grinding the sol into powder at 60 ℃ in a vacuum drying oven, and then placing the powder in a program-controlled high-temperature furnace for roasting to obtain the hydrophobic ZrO2-SiO2Composite adsorption material, in which it is calcinedThe parameters are as follows: in N2Heating to 400 ℃ at the speed of 3.0 ℃/min in the atmosphere, roasting for 3h, and naturally cooling to room temperature.
Example 5
(1) Fully mixing tetraethoxysilane, dimethyl diethoxysilane and absolute ethyl alcohol into a homogeneous solution, placing the homogeneous solution into an ice water mixture, adding a mixture of water and HCl with the concentration of 1.5mol/L while stirring, stirring and refluxing for 3 hours at the temperature of 65 ℃, and cooling to room temperature to obtain the methylated modified SiO2Sol; wherein the ethyl orthosilicate, the dimethyl diethoxysilane, the absolute ethyl alcohol, the water and the HNO3In a molar ratio of 1: 0.55: 12: 9: 0.1;
(2) dropwise adding oxalic acid solution with the concentration of 0.2mol/L into zirconium nitrate pentahydrate solution with the concentration of 0.5mol/L until the molar ratio of the zirconium nitrate pentahydrate solution to the oxalic acid solution is 5: stopping dripping at 1 hour, rapidly stirring, heating to 60 deg.C, mixing to obtain uniform liquid phase, maintaining temperature, adding glycerol under stirring, stirring and refluxing for 4 hr, and cooling to room temperature to obtain clear and transparent ZrO2Sol; wherein the volume of the glycerol is 20 percent of the sum of the volumes of the zirconium nitrate pentahydrate solution and the oxalic acid solution;
(3) taking the molar ratio of 0.8: 1 ZrO2Sol and methylated modified SiO2Sol, then methylating and modifying the SiO2Adding ZrO while stirring the sol2Rapidly stirring the mixed solution of the sol and the absolute ethyl alcohol for 40min to obtain hydrophobic ZrO2-SiO2Sol;
(4) hydrophobic ZrO2-SiO2Placing the sol in a culture dish, drying and grinding the sol into powder at 55 ℃ in a vacuum drying oven, and then placing the powder in a program-controlled high-temperature furnace for roasting to obtain the hydrophobic ZrO2-SiO2The composite adsorbing material comprises the following roasting parameters: in N2Heating to 450 deg.C at 2.0 deg.C/min in atmosphere, calcining for 2 hr, and naturally cooling to room temperature.
FIG. 1 shows the hydrophobic ZrO obtained in example 42-SiO2Composite adsorbent material and hydrophilic ZrO2-SiO2Composite adsorbing material, p-rhodamine B and methylene at pH 7 and T25 deg.CRemoval rates for blue and neutral red. As can be seen from FIG. 1, the hydrophobic ZrO2-SiO2The adsorption rate of the composite material to the three dyes is high; at 20min, the adsorption saturation is achieved, and the removal rate of the three dyes is more than or equal to 95 percent; hydrophilic ZrO2-SiO2The composite material basically reaches saturation in 20min, and the removal rate of the three dyes is only about 83%. Therefore, the methylation modification effectively improves the removal efficiency of the dye while maintaining the fast adsorption rate of the dye. Hydrophilic ZrO2-SiO2Composite adsorbent material (ZrO)2Sol and SiO2Sol molar ratio of 0.15) the final removal rates for the three dyes were 87.78%, 91.79%, 87.22%, respectively, and hydrophobic ZrO2-SiO2Composite adsorbent material (ZrO)2Sol and methylated modified SiO2Sol molar ratio of 0.15) final removal rates of 99.81%, 99.79%, 99.10% for the three dyes, respectively, by comparison, hydrophobic ZrO2-SiO2The removal rate of the composite adsorption material is greatly improved.
As shown in FIG. 2, the hydrophilic ZrO2-SiO2The adsorption capacity of the composite adsorption material to three dyes is respectively about 33.12, 36.71 and 39.88, and the hydrophobic ZrO2-SiO2The adsorption capacity of the composite adsorption material to the three dyes is 183.02, 213.56 and 216.48 respectively. As can be seen from FIG. 2, the hydrophobic ZrO2-SiO2Composite adsorption material is hydrophilic compared with ZrO2-SiO2The composite adsorbing material improves the adsorption capacity to rhodamine B.
By combining FIGS. 1 and 2, the hydrophobic ZrO of the present invention2-SiO2Composite adsorbent having hydrophilic ZrO inherited2-SiO2On the basis of better acid-base tolerance of the composite adsorption material, the removal efficiency of the dye and the adsorption capacity of the adsorbent are increased, and the adsorption performance is obviously improved.

Claims (5)

1. The preparation method of the hydrophobic zirconium dioxide-silicon dioxide composite adsorption material is characterized by comprising the following steps of:
in the step 1, the method comprises the following steps of,preparation of methylated modified SiO2Sol gel
Fully mixing tetraethoxysilane, dimethyl diethoxysilane and absolute ethyl alcohol into a homogeneous solution, putting the homogeneous solution into an ice-water mixture, adding water and HCl or HNO while stirring3Stirring and refluxing the mixture at the temperature of between 50 and 75 ℃ for 2 to 5 hours, and cooling to room temperature to obtain the methylated modified SiO2Dissolving the sol for later use;
the HCl or HNO3The concentration of the (A) is 1.0-2.0 mol/L;
the ethyl orthosilicate, the dimethyl diethoxysilane, the absolute ethyl alcohol, the water, the HCl or the HNO3In a molar ratio of 1: 0.4-0.6: 7.7-15.0: 7.3-12.0: 0.086-0.120;
step 2, preparation of ZrO2Sol gel
Adding a proper amount of oxalic acid solution into a zirconium nitrate pentahydrate solution dropwise, stirring quickly, heating to 50-70 ℃, mixing fully to form a uniform liquid phase, keeping the temperature, adding glycerol while stirring, stirring and refluxing for 2-4h, and cooling to normal temperature to obtain clear and transparent ZrO2Sol;
step 3, preparing hydrophobic ZrO2-SiO2Sol gel
Adding proper amount of the methylated modified SiO in the step 12Adding the ZrO obtained in the step 2 into the sol while stirring2Rapidly stirring the mixed solution of the sol and the absolute ethyl alcohol for 30-60min to obtain the hydrophobic ZrO2-SiO2Sol;
step 4, the hydrophobic ZrO prepared in the step 32-SiO2Placing the sol in a culture dish, drying and grinding the sol into powder in a vacuum drying oven, then placing the powder in a program-controlled high-temperature furnace, and roasting the powder at a certain temperature to obtain the hydrophobic ZrO2-SiO2Compounding the adsorption material;
the drying temperature is 30-60 ℃; the roasting parameters are as follows: heating to 350-450 deg.C at 1.0-5.0 deg.C/min in non-oxidizing gas atmosphere, calcining for 2-5h, and naturally cooling to room temperature.
2. The method for preparing a hydrophobic zirconium dioxide-silicon dioxide composite adsorption material according to claim 1, wherein the concentration of the zirconium nitrate pentahydrate solution in the step 2 is 0.2-0.6mol/L, and the concentration of the oxalic acid solution is 0.05-0.2 mol/L.
3. The method for preparing a hydrophobic zirconium dioxide-silicon dioxide composite adsorption material according to claim 2, wherein the molar ratio of the zirconium nitrate pentahydrate solution to the oxalic acid solution in the step 2 is 4.0-5.0: 1.
4. The method for preparing a hydrophobic zirconia-silica composite adsorbent according to claim 2, wherein the volume of glycerol in the step 2 is 20 to 35% of the sum of the volumes of the zirconium nitrate pentahydrate solution and the oxalic acid solution.
5. The method according to claim 4, wherein ZrO in the step 3 is selected from the group consisting of2Sol and methylated modified SiO2The molar ratio of the sol is 0.05-1.0: 1.
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CN114797803A (en) * 2022-06-28 2022-07-29 南通纳爱斯环保科技有限公司 Modified polyphenylsulfone filtering membrane applied to arsenic removal and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1757598A (en) * 2005-10-26 2006-04-12 太原理工大学 Method for preparing super fine hydrophobic silicon dioxide
CN102765725A (en) * 2012-08-10 2012-11-07 蓝烟（北京）科技有限公司 Method for preparing hydrophobic silica aerogel with low cost

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1757598A (en) * 2005-10-26 2006-04-12 太原理工大学 Method for preparing super fine hydrophobic silicon dioxide
CN102765725A (en) * 2012-08-10 2012-11-07 蓝烟（北京）科技有限公司 Method for preparing hydrophobic silica aerogel with low cost

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Al2O3-SiO2复合膜的疏水改性及表征";同帜，等;《材料科学与工程学报》;20141031;第32卷(第5期);第741-744页 *
"Silica-Zirconia Sol–Gel Coatings Obtained by Different Synthesis Routes";Y. CASTRO，et al;<Journal of Sol-Gel Science and Technology>;20051231;第35卷;第41-50页 *

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