CN110614076A - Preparation method of zirconium dioxide/aluminum oxide composite adsorption material - Google Patents

Preparation method of zirconium dioxide/aluminum oxide composite adsorption material Download PDF

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CN110614076A
CN110614076A CN201910974085.6A CN201910974085A CN110614076A CN 110614076 A CN110614076 A CN 110614076A CN 201910974085 A CN201910974085 A CN 201910974085A CN 110614076 A CN110614076 A CN 110614076A
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aluminum oxide
zirconium dioxide
sol
oxide composite
stirring
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杨靖
王茜
徐志润
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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
    • B01J20/06—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
    • B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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

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Abstract

The invention relates to a preparation method of a zirconium dioxide/aluminum oxide composite adsorption material, which specifically comprises the following steps: step 1: obtaining zirconium dioxide sol; step 2: obtaining alumina sol; and step 3: obtaining zirconium dioxide/aluminum oxide composite adsorption sol; and 4, step 4: and (3) carrying out vacuum drying, roasting and cooling on the zirconium dioxide/aluminum oxide composite adsorption sol, and then grinding the zirconium dioxide/aluminum oxide composite adsorption sol into powder to obtain the zirconium dioxide/aluminum oxide composite adsorption material. According to the preparation method of the zirconium dioxide/aluminum oxide composite adsorption material, the zirconium dioxide/aluminum oxide composite adsorption material prepared by adopting a sol-sol method improves the adsorption capacity and the adsorption efficiency of printing and dyeing wastewater and the like.

Description

Preparation method of zirconium dioxide/aluminum oxide composite adsorption material
Technical Field
The invention belongs to the technical field of adsorption materials, and particularly relates to a preparation method of a zirconium dioxide/aluminum oxide composite adsorption material.
Background
In recent years, the dye yield of China is the first place in the world. During the production and processing of the dye, about 10 to 20 percent of the dye is discharged with the waste water, and the dye waste water becomes one of the main pollution sources of the water body. Therefore, the treatment of the dye wastewater is the focus of attention in the chemical industry and the environmental protection industry in recent years, and the treatment of the dye wastewater is not slow. The dye wastewater has the characteristics of high organic pollutant content, violent water quality change, various dyes, large pH value change and the like. Various synthetic dyes, such as azo dyes, polymeric dyes, anthraquinone dyes, triphenylmethane dyes and heterocyclic dyes, are used in textile dyeing processes. The synthetic dye can prevent sunlight from irradiating into water, so that water eutrophication and animal and plant death are caused, and serious environmental problems are caused when industrial dye wastewater is continuously discharged into natural rivers. Synthetic dyes are therefore considered to be one of the toxic and harmful compounds in water, soil and human life.
Since a large amount of wastewater discharged from the printing and dyeing industry can bring serious threats to the ecological environment and human health, the treatment of printing and dyeing wastewater is always a hot point of research at home and abroad. The physical adsorption method is widely applied to the treatment of dye wastewater due to the advantages of high removal rate, low cost, high dye decolorization rate, convenient subsequent treatment and the like. The common adsorbents include activated carbon, molecular sieves, adsorbent resins and other adsorbent materials. In summary, the conventional zirconia material or alumina material has the problems of low adsorption capacity and low adsorption efficiency.
Disclosure of Invention
The invention aims to provide a preparation method of a zirconium dioxide/aluminum oxide composite adsorption material, which solves the problems of low adsorption capacity and low adsorption efficiency of the existing zirconium dioxide material or aluminum oxide material.
The technical scheme adopted by the invention is that,
a preparation method of a zirconium dioxide/aluminum oxide composite adsorption material specifically comprises the following steps:
step 1: obtaining a zirconium dioxide sol, which comprises the following steps:
step 11: preparing an oxalic acid solution of zirconium nitrate:
wherein the molar ratio of zirconium nitrate to oxalic acid in the oxalic acid solution is 1.5-4.5: 1;
step 12: adding an oxalic acid solution into a zirconium nitrate pentahydrate solution, and heating and stirring to obtain a homogeneous solution;
step 13: dripping glycerol into the homogeneous phase solution, stirring, refluxing and cooling to obtain zirconium dioxide sol;
step 2: obtaining alumina sol, wherein the steps specifically comprise:
step 21, heating pure water, and adding the pure water in a molar ratio of 1: 80-1: 160 of aluminium isopropoxide to obtain an aqueous solution of isopropanol;
step 22: adding a nitric acid solution with the concentration of 1.0-4.0 mol/L into an isopropanol aqueous solution, and stirring and refluxing to obtain an aluminum oxide sol;
and step 3: the method comprises the following steps of (1) obtaining zirconium dioxide/aluminum oxide composite adsorption sol, wherein the steps specifically comprise:
step 31: adding the alumina sol obtained in the step 13 into absolute ethyl alcohol to obtain a mixed solution;
step 32: dropwise adding the zirconium dioxide sol obtained in the step (23) and aluminum oxide into the mixed solution according to the molar ratio of 1: 0.05-1: 2 to obtain a zirconium dioxide/aluminum oxide composite adsorption sol;
and 4, step 4: and (3) carrying out vacuum drying, roasting and cooling on the zirconium dioxide/aluminum oxide composite adsorption sol, and then grinding the zirconium dioxide/aluminum oxide composite adsorption sol into powder to obtain the zirconium dioxide/aluminum oxide composite adsorption material.
The invention is also characterized in that;
in step 3, the zirconium dioxide sol and the aluminum oxide sol in the zirconium dioxide/aluminum oxide composite adsorption sol are mixed according to the following mass percentage:
zirconium dioxide: 66.7 to 33.3 percent; aluminum oxide: 33.3 to 66.7 percent.
In the step 1, the concentration of the oxalic acid solution is 0.15-0.2 mol/L, the concentration of the zirconium nitrate pentahydrate solution is 0.55-0.6 mol/L, and the added glycerol accounts for 30-40% of the volume fraction of the homogeneous solution.
In the step 1, heating and stirring comprise rapid stirring and heating to 50-70 ℃, wherein the stirring speed is 12-17 r/s; the stirring and refluxing time is controlled to be 2-4 h.
In step 2, heating pure water by using a heat collection type constant-temperature magnetic stirrer, dropwise adding a nitric acid solution into an isopropanol aqueous solution by using a constant-pressure funnel, wherein the adding amount of the nitric acid solution is controlled as follows: after adding the nitric acid solution, the molar ratio of nitric acid to water in the solution is 0.15: 1-0.45: 1.
in the step 2, the pure water is heated to 75-85 ℃, the temperature of stirring reflux is controlled to 80-90 ℃, and the time is controlled to 7.0-9.0 h.
In step 3, the experiment was subjected to the following parameter control: adding the zirconium dioxide sol into the mixed solution at a dropping speed of 0.05-0.15 mL/s, and stirring for 30-60 min at the laboratory environment temperature, wherein the stirring speed is 7-13 r/s.
In step 4, the experiment was subjected to the following parameter control: the vacuum drying time is 15-25 days, the mixture is taken out and is heated to 400-800 ℃ at a speed of 0.5-5 ℃/min in the air atmosphere, the mixture is roasted for 1-6 hours, the mixture is cooled to the environmental temperature of a laboratory at a speed of 1-10 ℃/min, and the ground particle size is 1-20 nm.
In step 4, the atmosphere after the removal is nitrogen.
The preparation method of the zirconium dioxide/aluminum oxide composite adsorption material has the beneficial effects that the zirconium dioxide/aluminum oxide composite adsorption material is obtained by adopting a sol-sol method, so that the adsorption capacity and the adsorption efficiency of the existing zirconium dioxide material and aluminum oxide material to printing and dyeing wastewater are improved.
Drawings
FIG. 1 is a schematic diagram showing the comparison of the adsorption capacities of a zirconium dioxide/aluminum oxide composite adsorption material, an aluminum oxide material and a zirconium dioxide material to a dye in a preparation method of the zirconium dioxide/aluminum oxide composite adsorption material according to the present invention;
FIG. 2 is a comparison of the adsorption efficiency of the zirconium dioxide/aluminum oxide composite adsorption material, the aluminum oxide material and the zirconium dioxide material to dyes, etc. in the preparation method of the zirconium dioxide/aluminum oxide composite adsorption material of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
Zirconium dioxide/aluminum oxide composite adsorption material (ZrO)2/Al2O3) The preparation method specifically comprises the following steps:
step 1: obtaining zirconium dioxide (ZrO)2) Sol, which comprises the following steps:
step 11: preparing an oxalic acid solution of zirconium nitrate:
wherein the molar ratio of zirconium nitrate to oxalic acid in the oxalic acid solution is 1.5-4.5: 1;
step 12: adding an oxalic acid solution into a zirconium nitrate pentahydrate solution, and heating and stirring to obtain a homogeneous solution;
step 13: dripping glycerol into the homogeneous phase solution, stirring, refluxing and cooling to obtain zirconium dioxide sol;
step 2: obtaining the aluminum oxide (Al)2O3) Sol, which comprises the following steps:
step 21, heating pure water, and adding the pure water in a molar ratio of 1: 80-1: 160 of aluminium isopropoxide to obtain an aqueous solution of isopropanol;
step 22: adding a nitric acid solution with the concentration of 1.0-4.0 mol/L into an isopropanol aqueous solution, and stirring and refluxing to obtain an aluminum oxide sol;
and step 3: the method comprises the following steps of (1) obtaining zirconium dioxide/aluminum oxide composite adsorption sol, wherein the steps specifically comprise:
step 31: adding the alumina sol obtained in the step 13 into absolute ethyl alcohol to obtain a mixed solution;
step 32: dropwise adding the zirconium dioxide sol obtained in the step (23) and aluminum oxide into the mixed solution according to the molar ratio of 1: 0.05-1: 2 to obtain a zirconium dioxide/aluminum oxide composite adsorption sol;
and 4, step 4: and (3) carrying out vacuum drying, roasting and cooling on the zirconium dioxide/aluminum oxide composite adsorption sol, and then grinding the zirconium dioxide/aluminum oxide composite adsorption sol into powder to obtain the zirconium dioxide/aluminum oxide composite adsorption material.
Further, in step 3, the zirconium dioxide sol and the aluminum oxide sol in the zirconium dioxide/aluminum oxide composite adsorption sol are mixed according to the following mass percentage:
zirconium dioxide: 66.7 to 33.3 percent; aluminum oxide: 33.3 to 66.7 percent.
Further, in the step 1, the concentration of the oxalic acid solution is 0.15-0.2 mol/L, the concentration of the zirconium nitrate pentahydrate solution is 0.55-0.6 mol/L, and the amount of the added glycerol is 30-40% of the volume fraction of the homogeneous phase solution.
Further, in the step 1, the heating and stirring include rapid stirring and heating to 50-70 ℃, wherein the stirring speed is 12-17 r/s; the stirring and refluxing time is controlled to be 2-4 h.
Further, in step 2, heating pure water by using a heat collection type constant temperature magnetic stirrer, and dropwise adding a nitric acid solution into the isopropanol aqueous solution by using a constant pressure funnel, wherein the adding amount of the nitric acid solution is controlled as follows: after adding the nitric acid solution, the molar ratio of nitric acid to water in the solution is 0.15: 1-0.45: 1.
further, in the step 2, the pure water is heated to 75-85 ℃, the temperature of stirring reflux is controlled to 80-90 ℃, and the time is controlled to 7.0-9.0 h.
Further, in step 3, the experiment was subjected to the following parameter control: adding the zirconium dioxide sol into the mixed solution at a dropping speed of 0.05-0.15 mL/s, and stirring for 30-60 min at the laboratory environment temperature, wherein the stirring speed is 7-13 r/s.
Further, in step 4, the experiment was subjected to the following parameter control: the vacuum drying time is 15-25 days, the mixture is taken out and is heated to 400-800 ℃ at a speed of 0.5-5 ℃/min in the air atmosphere, the mixture is roasted for 1-6 hours, the mixture is cooled to the environmental temperature of a laboratory at a speed of 1-10 ℃/min, and the ground particle size is 1-20 nm.
Further, in step 4, the atmosphere after the removal is nitrogen.
ZrO prepared by the method in step 1 and step 22Sol, Al2O3Sol, then treating the sol and the sol respectively as in step 4 to obtainZrO2Adsorbing material and Al2O3Adsorbing material; preparation of ZrO by reusing the above method2/Al2O3The adsorption capacity of the three materials to the dye is compared.
As shown in FIG. 1, is ZrO produced according to the present invention2/Al2O3Composite adsorbent and Al2O3Material and ZrO2Adsorption capacity of materials versus dyes is plotted. Al (Al)2O3Material and ZrO2The adsorption capacities of the materials are 2.798mg/g and 3.655mg/g respectively, ZrO2/Al2O3The adsorption capacity of the composite adsorption material is 9.323mg/g, compared with the ZrO prepared by the invention2/Al2O3The adsorption capacity of the composite adsorption material is respectively improved by 6.525mg/g and 5.668 mg/g.
As shown in FIG. 2, is ZrO produced by the present invention2/Al2O3Composite adsorbent and Al2O3Material and ZrO2The adsorption efficiency of the material to the dye is compared. Al (Al)2O3Material and ZrO2The adsorption efficiencies of the materials are respectively 27.98% and 36.55%, ZrO2/Al2O3Compared with the ZrO prepared by the invention, the adsorption efficiency of the composite adsorption material is 93.23 percent2/Al2O3The adsorption efficiency of the composite adsorption material is respectively improved by 65.25% and 56.68%.
The zirconium dioxide/aluminum oxide composite adsorption material prepared by the preparation method can effectively improve the adsorption capacity and the adsorption efficiency of printing and dyeing wastewater and the like.
Example 1
The following describes in detail a method for preparing a zirconium dioxide/aluminum oxide composite adsorption material according to the present invention with specific examples:
step 1, adding zirconium nitrate and oxalic acid according to the molar ratio: 1.5:1, adding 0.15mol/L oxalic acid solution into 0.55mol/L zirconium nitrate pentahydrate solution, rapidly stirring and heating to 50 ℃, wherein the stirring speed is 12r/s, fully mixing to obtain a homogeneous solution, keeping the temperature, dropwise adding glycerol with the volume fraction of 30 percent of the homogeneous solution at the speed of 0.05mL/s while stirring, stirring and refluxing for 4 hours, and cooling to the ambient temperature of a laboratory to obtain clear and transparent ZrO2Sol;
step 2, heating pure water to 75 ℃ by using a heat collection type constant temperature magnetic stirrer according to the molar ratio of Aluminum Isopropoxide (AIP), water and nitric acid of 1:80:0.15, adding weighed aluminum isopropoxide into water and stirring for 3 hours at the stirring speed of 15r/s, fully hydrolyzing, and then using a constant pressure funnel to obtain HNO with the concentration of 1.0mol/L3Slowly adding into the reacted system, stirring and refluxing at 80 deg.C for 7.0 hr to obtain stable and transparent Al2O3Sol;
step 3, ZrO according to a molar ratio2:Al2O31:0.05, mixing the prepared ZrO2Al is added dropwise to the sol at a rate of 0.05mL/s2O3Stirring the mixed solution of the sol and the absolute ethyl alcohol for 30min at the rotating speed of 7r/s at the environmental temperature of a laboratory to obtain ZrO2/Al2O3Compounding adsorption sol.
Step 4, drying the prepared composite adsorption sol in vacuum at the temperature of 110 ℃ for 15 days, then heating to 400 ℃ at the speed of 0.5 ℃/min in the air atmosphere, roasting for 2 hours, cooling to the environmental temperature of a laboratory at the speed of 1 ℃/min, grinding the powder into powder with the particle size of 1nm to obtain ZrO2/Al2O3And (3) compounding the adsorption material.
Example 2
The following describes in detail a method for preparing a zirconium dioxide/aluminum oxide composite adsorption material according to the present invention with specific examples:
step 1, according to the molar ratio of zirconium nitrate to oxalic acid: 3:1, adding 0.18mol/L oxalic acid solution into 0.58mol/L zirconium nitrate pentahydrate solution, rapidly stirring and heating to 60 ℃, stirring at the speed of 15r/s, fully mixing to obtain homogeneous solution, keeping the temperature, dropwise adding glycerol with the volume fraction of 30 percent of that of the homogeneous solution at the speed of 0.10mL/s while stirring, stirring and refluxing for 3 hours, and cooling to be solidAt the ambient temperature of the laboratory, clear and transparent ZrO can be obtained2Sol;
step 2, heating pure water to 80 ℃ by using a heat collection type constant temperature magnetic stirrer according to the molar ratio of Aluminum Isopropoxide (AIP), water and nitric acid of 1:120:0.3, adding weighed aluminum isopropoxide into water and stirring for 2 hours at the stirring speed of 17r/s, fully hydrolyzing, and then using a constant pressure funnel to obtain HNO with the concentration of 2.0mol/L3Slowly adding into the reacted system, stirring and refluxing at 85 deg.C for 8.0 hr to obtain stable and transparent Al2O3Sol;
step 3, ZrO according to a molar ratio2:Al2O31:1, mixing the prepared ZrO2Al is added dropwise into the sol at a rate of 0.1mL/s2O3Stirring in a mixed solution of sol and absolute ethyl alcohol at the rotating speed of 13r/s for 45min at the environmental temperature of a laboratory to obtain ZrO2/Al2O3Compounding adsorption sol.
Step 4, preparing the prepared ZrO2/Al2O3Vacuum drying the composite adsorption sol at 85 deg.C for 20 days, heating to 500 deg.C at 4 deg.C/min in nitrogen atmosphere, calcining for 4.5 hr, cooling to laboratory environment at 5 deg.C/min, and grinding into powder with particle size of 5nm to obtain ZrO2/Al2O3And (3) compounding the adsorption material.
Example 3
The following describes in detail a method for preparing a zirconium dioxide/aluminum oxide composite adsorption material according to the present invention with specific examples:
step 1, according to the molar ratio of zirconium nitrate to oxalic acid: 4.5:1, adding 0.2mol/L oxalic acid solution into 0.6mol/L zirconium nitrate pentahydrate solution, quickly stirring and heating to 70 ℃, stirring at the speed of 17r/s, fully mixing to obtain homogeneous solution, keeping the temperature, dropwise adding glycerol with the volume fraction of 40% at the speed of 0.15mL/s while stirring, stirring and refluxing for 2h, and cooling to the ambient temperature of a laboratory to obtain clear and transparent ZrO2Sol;
step 2, Aluminum Isopropoxide (AIP), water and nitre are addedThe mol ratio of the acid is 1:160:0.45, pure water is heated to 85 ℃ by a heat collection type constant temperature magnetic stirrer, weighed aluminum isopropoxide is added into the water and stirred for 1h, the stirring speed is 15r/s, HNO with the concentration of 4.0mol/L is fully hydrolyzed by a constant pressure funnel3Slowly adding into the reacted system, stirring and refluxing at 90 deg.C for 9.0 hr to obtain stable and transparent Al2O3Sol;
step 3, ZrO according to a molar ratio2:Al2O31:2, the ZrO prepared in step 12Al is added dropwise into the sol at a speed of 0.15mL/s2O3Stirring the mixed solution of the sol and the absolute ethyl alcohol for 60min at the rotating speed of 10r/s at the environmental temperature of a laboratory to obtain ZrO2/Al2O3Compounding adsorption sol.
Step 4, preparing the prepared ZrO2/Al2O3Vacuum drying the composite adsorption sol at 60 deg.C for 25 days, heating to 600 deg.C at 2 deg.C/min in nitrogen atmosphere, calcining for 2.5 hr, cooling to laboratory environment at 10 deg.C/min, and grinding into powder with particle size of 10nm to obtain ZrO2/Al2O3And (3) compounding the adsorption material.
Example 4
The following describes in detail a method for preparing a zirconium dioxide/aluminum oxide composite adsorption material according to the present invention with specific examples:
step 1, according to the molar ratio of zirconium nitrate to oxalic acid: 1.5:1, adding 0.15mol/L oxalic acid solution into 0.55mol/L zirconium nitrate pentahydrate solution, quickly stirring and heating to 60 ℃, stirring at the speed of 16r/s, fully mixing to obtain homogeneous solution, keeping the temperature, dropwise adding glycerol with the volume fraction of 30 percent of the homogeneous solution at the speed of 0.1mL/s while stirring, stirring and refluxing for 3 hours, and cooling to the ambient temperature of a laboratory to obtain clear and transparent ZrO2Sol;
step 2, heating the pure water to 80 ℃ by utilizing a heat collection type constant temperature magnetic stirrer according to the molar ratio of Aluminum Isopropoxide (AIP), water and nitric acid of 1:80:0.15, and adding the weighed aluminum isopropoxide into the waterNeutralizing and stirring for 2h at a stirring speed of 15r/s, sufficiently hydrolyzing, and adding HNO with a concentration of 1mol/L by using a constant pressure funnel3Slowly adding into the reacted system, stirring and refluxing at 85 deg.C for 8 hr to obtain stable and transparent Al2O3Sol;
step 3, ZrO according to a molar ratio2:Al2O31:0.05, mixing the prepared ZrO2Al is added dropwise to the sol at a rate of 0.05mL/s2O3Stirring the mixed solution of the sol and the absolute ethyl alcohol for 30min at the rotating speed of 7r/s at the environmental temperature of a laboratory to obtain ZrO2/Al2O3Compounding adsorption sol.
Step 4, preparing the prepared ZrO2/Al2O3Vacuum drying the composite adsorption sol at 110 deg.C for 15 days, heating to 400 deg.C at 0.5 deg.C/min in air atmosphere, calcining for 2 hr, cooling to laboratory environment temperature at 1 deg.C/min, and grinding into powder with particle size of 1nm to obtain ZrO2/Al2O3And (3) compounding the adsorption material.
Example 5
The following describes in detail a method for preparing a zirconium dioxide/aluminum oxide composite adsorption material according to the present invention with specific examples:
step 1, according to the molar ratio of zirconium nitrate to oxalic acid: 1.5:1, adding 0.15mol/L oxalic acid solution into 0.5mol/L zirconium nitrate pentahydrate solution, quickly stirring and heating to 70 ℃, stirring at the speed of 17r/s, fully mixing to obtain homogeneous solution, keeping the temperature, dropwise adding glycerol with the volume fraction of 30 percent of the homogeneous solution at the speed of 0.1mL/s while stirring, stirring and refluxing for 3 hours, and cooling to the ambient temperature of a laboratory to obtain clear and transparent ZrO2Sol;
step 2, heating pure water to 85 ℃ by using a heat collection type constant temperature magnetic stirrer according to the molar ratio of Aluminum Isopropoxide (AIP), water and nitric acid of 1:80:0.15, adding weighed aluminum isopropoxide into water and stirring for 3 hours at the stirring speed of 17r/s, fully hydrolyzing, and then using a constant pressure funnel to obtain HNO with the concentration of 1.0mol/L3Slowly adding into the reacted systemRefluxing at 90 deg.C under stirring for 9.0 hr to obtain stable and transparent Al2O3Sol;
step 3, ZrO according to a molar ratio2:Al2O31:0.05, mixing the prepared ZrO2Al is added dropwise to the sol at a rate of 0.05mL/s2O3Stirring in a mixed solution of sol and absolute ethyl alcohol at the rotating speed of 11r/s for 30min at the environmental temperature of a laboratory to obtain ZrO2/Al2O3Compounding adsorption sol.
Step 4, preparing the prepared ZrO2/Al2O3Vacuum drying the composite adsorption sol at 110 deg.C for 15 days, heating to 400 deg.C at 0.5 deg.C/min in air atmosphere, calcining for 2 hr, cooling to laboratory environment temperature at 1 deg.C/min, and grinding into powder with particle size of 1nm to obtain ZrO2/Al2O3And (3) compounding the adsorption material.
Example 6
The following describes in detail a method for preparing a zirconium dioxide/aluminum oxide composite adsorption material according to the present invention with specific examples:
step 1, according to the molar ratio of zirconium nitrate to oxalic acid: 3.5:1, adding 0.2mol/L oxalic acid solution into 0.55mol/L zirconium nitrate pentahydrate solution, quickly stirring and heating to 65 ℃, stirring at the speed of 16r/s, fully mixing to obtain homogeneous solution, keeping the temperature, dropwise adding glycerol with the volume fraction of 30 percent of the homogeneous solution at the speed of 0.12mL/s while stirring, stirring and refluxing for 3 hours, and cooling to the ambient temperature of a laboratory to obtain clear and transparent ZrO2Sol;
step 2, heating pure water to 85 ℃ by using a heat collection type constant temperature magnetic stirrer according to the molar ratio of Aluminum Isopropoxide (AIP), water and nitric acid of 1:110:0.15, adding weighed aluminum isopropoxide into water and stirring for 3 hours at the stirring speed of 17r/s, fully hydrolyzing, and then using a constant pressure funnel to obtain HNO with the concentration of 1.0mol/L3Slowly adding into the reacted system, stirring and refluxing at 90 deg.C for 9.0 hr to obtain stable and transparent Al2O3Sol;
step 3, ZrO according to a molar ratio2:Al2O31:1.3, mixing the prepared ZrO2Al is added dropwise to the sol at a rate of 0.05mL/s2O3Stirring in a mixed solution of sol and absolute ethyl alcohol at the rotating speed of 11r/s for 30min at the environmental temperature of a laboratory to obtain ZrO2/Al2O3Compounding adsorption sol.
Step 4, preparing the prepared ZrO2/Al2O3Vacuum drying the composite adsorption sol at 110 deg.C for 15 days, heating to 400 deg.C at 0.5 deg.C/min in air atmosphere, calcining for 2 hr, cooling to laboratory environment temperature at 1 deg.C/min, and grinding into powder with particle size of 1nm to obtain ZrO2/Al2O3And (3) compounding the adsorption material.
Example 7
The following describes in detail a method for preparing a zirconium dioxide/aluminum oxide composite adsorption material according to the present invention with specific examples:
step 1, according to the molar ratio of zirconium nitrate to oxalic acid: 2.2:1, adding 0.16mol/L oxalic acid solution into 0.58mol/L zirconium nitrate pentahydrate solution, quickly stirring and heating to 55 ℃, stirring at the speed of 12r/s, fully mixing to obtain homogeneous solution, keeping the temperature, dropwise adding glycerol with the volume fraction of 30 percent of the homogeneous solution at the speed of 0.15mL/s while stirring, stirring and refluxing for 3 hours, and cooling to the ambient temperature of a laboratory to obtain clear and transparent ZrO2Sol;
step 2, heating pure water to 80 ℃ by using a heat collection type constant temperature magnetic stirrer according to the molar ratio of Aluminum Isopropoxide (AIP), water and nitric acid of 1:150:0.15, adding weighed aluminum isopropoxide into water and stirring for 2 hours at the stirring speed of 16r/s, fully hydrolyzing, and then using a constant pressure funnel to obtain HNO with the concentration of 1.0mol/L3Slowly adding into the reacted system, stirring and refluxing at 90 deg.C for 8.0 hr to obtain stable and transparent Al2O3Sol;
step 3, ZrO according to a molar ratio2:Al2O31:0.7, mixing the prepared ZrO2Al is added dropwise to the sol at a rate of 0.05mL/s2O3Stirring in a mixed solution of sol and absolute ethyl alcohol at the rotating speed of 11r/s for 45min at the environmental temperature of a laboratory to obtain ZrO2/Al2O3Compounding adsorption sol.
Step 4, preparing the prepared ZrO2/Al2O3Vacuum drying the composite adsorption sol at 110 deg.C for 21 days, heating to 400 deg.C at 3 deg.C/min in air atmosphere, calcining for 3 hr, cooling to laboratory environment temperature at 7 deg.C/min, and grinding into powder with particle diameter of 7nm to obtain ZrO2/Al2O3And (3) compounding the adsorption material.
The invention relates to a preparation method of a zirconium dioxide/aluminum oxide composite adsorption material, which respectively obtains ZrO through a sol-sol method2And Al2O3Sol, and then obtaining ZrO through operation of a certain proportion2/Al2O3Composite adsorption material, ZrO produced thereby2/Al2O3The composite adsorption material has greatly improved adsorption capacity and adsorption efficiency on printing and dyeing wastewater and the like, and has stronger practicability.

Claims (9)

1. A preparation method of a zirconium dioxide/aluminum oxide composite adsorption material is characterized by comprising the following steps:
step 1: obtaining a zirconium dioxide sol, which comprises the following steps:
step 11: preparing an oxalic acid solution of zirconium nitrate:
wherein the molar ratio of zirconium nitrate to oxalic acid in the oxalic acid solution is 1.5-4.5: 1;
step 12: adding an oxalic acid solution into a zirconium nitrate pentahydrate solution, and heating and stirring to obtain a homogeneous solution;
step 13: dripping glycerol into the homogeneous phase solution, stirring, refluxing and cooling to obtain zirconium dioxide sol;
step 2: obtaining alumina sol, wherein the steps specifically comprise:
step 21, heating pure water, and adding the pure water in a molar ratio of 1: 80-1: 160 of aluminium isopropoxide to obtain an aqueous solution of isopropanol;
step 22: adding a nitric acid solution with the concentration of 1.0-4.0 mol/L into an isopropanol aqueous solution, and stirring and refluxing to obtain an aluminum oxide sol;
and step 3: the method comprises the following steps of (1) obtaining zirconium dioxide/aluminum oxide composite adsorption sol, wherein the steps specifically comprise:
step 31: adding the alumina sol obtained in the step 13 into absolute ethyl alcohol to obtain a mixed solution;
step 32: dropwise adding the zirconium dioxide sol obtained in the step (23) and aluminum oxide into the mixed solution according to the molar ratio of 1: 0.05-1: 2 to obtain a zirconium dioxide/aluminum oxide composite adsorption sol;
and 4, step 4: and (3) carrying out vacuum drying, roasting and cooling on the zirconium dioxide/aluminum oxide composite adsorption sol, and then grinding the zirconium dioxide/aluminum oxide composite adsorption sol into powder to obtain the zirconium dioxide/aluminum oxide composite adsorption material.
2. The preparation method of the zirconium dioxide/aluminum oxide composite adsorption material according to claim 1, wherein in step 3, the zirconium dioxide sol and the aluminum oxide sol in the zirconium dioxide/aluminum oxide composite adsorption sol are mixed according to the following mass percentages:
zirconium dioxide: 66.7 to 33.3 percent; aluminum oxide: 33.3 to 66.7 percent.
3. The preparation method of the zirconium dioxide/aluminum oxide composite adsorbing material as claimed in claim 1, wherein in the step 1, the concentration of the oxalic acid solution is 0.15-0.2 mol/L, the concentration of the zirconium nitrate pentahydrate solution is 0.55-0.6 mol/L, and the amount of the added glycerol is 30-40% of the volume fraction of the homogeneous solution.
4. The preparation method of the zirconium dioxide/aluminum oxide composite adsorbing material as claimed in claim 1, wherein in the step 1, the heating and stirring comprises rapid stirring and heating to 50-70 ℃, and the stirring speed is 12-17 r/s; and the stirring and refluxing time is controlled to be 2-4 h.
5. The preparation method of the zirconium dioxide/aluminum oxide composite adsorption material according to claim 1, wherein in the step 2, a heat collection type constant temperature magnetic stirrer is used for heating pure water, a constant pressure funnel is used for dropwise adding a nitric acid solution into an isopropanol aqueous solution, and the adding amount of the nitric acid solution is controlled as follows: after adding the nitric acid solution, the molar ratio of nitric acid to water in the solution is 0.15: 1-0.45: 1.
6. the preparation method of the zirconium dioxide/aluminum oxide composite adsorbing material as claimed in claim 5, wherein in the step 2, the pure water is heated to 75-85 ℃, the temperature of stirring and refluxing is controlled to 80-90 ℃, and the time is controlled to 7.0-9.0 h.
7. The method for preparing the zirconium dioxide/aluminum oxide composite adsorbing material according to claim 1, wherein in the step 3, the following parameters are controlled: adding the zirconium dioxide sol into the mixed solution at a dropping speed of 0.05-0.15 mL/s, and stirring for 30-60 min at the laboratory environment temperature, wherein the stirring speed is 7-13 r/s.
8. The method for preparing the zirconium dioxide/aluminum oxide composite adsorbing material according to claim 1, wherein in the step 4, the following parameters are controlled: the vacuum drying time is 15-25 days, the mixture is taken out and is heated to 400-800 ℃ at a speed of 0.5-5 ℃/min in the air atmosphere, the mixture is roasted for 1-6 hours, the mixture is cooled to the environmental temperature of a laboratory at a speed of 1-10 ℃/min, and the ground particle size is 1-20 nm.
9. The method for preparing the zirconium dioxide/aluminum oxide composite adsorbing material according to claim 8, wherein in the step 4, the atmosphere after being taken out is nitrogen.
CN201910974085.6A 2019-10-14 2019-10-14 Preparation method of zirconium dioxide/aluminum oxide composite adsorption material Pending CN110614076A (en)

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Application publication date: 20191227