CN112982029B - ZrO for high-density solvent oil/water separation 2 Preparation method of filter paper - Google Patents
ZrO for high-density solvent oil/water separation 2 Preparation method of filter paper Download PDFInfo
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- CN112982029B CN112982029B CN202110156028.4A CN202110156028A CN112982029B CN 112982029 B CN112982029 B CN 112982029B CN 202110156028 A CN202110156028 A CN 202110156028A CN 112982029 B CN112982029 B CN 112982029B
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/08—Filter paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/13—Silicon-containing compounds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/02—Chemical or biochemical treatment
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/04—Physical treatment, e.g. heating, irradiating
- D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
Abstract
The invention discloses a ZrO for separating high-density solvent oil/water 2 The preparation method of the filter paper comprises the following steps: step 1, preparing ZrO 2 Sol; step 2, soaking the filter paper with clean surface in the prepared ZrO at room temperature 2 In the sol, taking out the filter paper, centrifuging and drying, and depositing a layer of ZrO on the surface of the filter paper 2 Gel; step 3, coating ZrO on the surface of the filter paper by adopting a sol-gel method/low-temperature photochemical degradation synergistic process 2 Gel layer is transformed into amorphous ZrO 2 A ceramic layer; step 4, preparing a low surface energy chemical modifier solution, and depositing ZrO on the surface 2 Soaking the filter paper of the ceramic layer in chemical modifier for a period of time, taking out the filter paper, washing and drying to obtain ZrO for high-density solvent oil/water separation 2 /filter paper. Solves the problems of the prior art that the filter paper material has poor recycling performance and poor acid/alkali resistance stability in oil-water separation.
Description
Technical Field
The invention belongs to the technical field of oil-water separation, and relates to ZrO for high-density solvent oil/water separation 2 Preparation method of filter paper.
Background
As a special paper-based material, the filter paper has the advantages of high mechanical strength, high porosity, good filtering effect and the like compared with common paper, and is widely applied to production and life. After the super-hydrophobic/super-oleophilic surface is constructed on the filter paper, the filter paper can be applied to the field of oil-water separation. Compared with the traditional oil-water separation modes such as gravity separation, the filter paper is adopted for oil-water separation, so that the efficiency is higher and the selectivity is stronger.
At present, the method adopted for constructing the super-hydrophobic/super-oleophylic surface on the filter paper generally comprises the steps of firstly preparing nano particles, then carrying out silanization modification on the nano particles, and finally fixing the nano particles on the filter paper. The method has complicated steps, and the binding force between the nano particles and the filter paper is poor, so that the filter paper material has poor recycling performance in oil-water separation, and the oil-water separation function is extremely easy to lose in corrosive media such as acid/alkali.
Disclosure of Invention
The object of the present invention is to provide a ZrO for high-density solvent oil/water separation 2 The preparation method of the filter paper solves the problems of poor recycling performance and poor acid/alkali resistance stability of the filter paper material in oil-water separation in the prior art.
The technical proposal adopted by the invention is that the ZrO for separating the high-density solvent oil/water 2 The preparation method of the filter paper comprises the following steps:
step 1, preparing ZrO 2 Sol;
step 2, soaking the filter paper with clean surface in the prepared ZrO at room temperature 2 In the sol, taking out the filter paper, centrifuging and drying, and depositing a layer of ZrO on the surface of the filter paper 2 Gel;
step 3, coating ZrO on the surface of the filter paper by adopting a sol-gel method/low-temperature photochemical degradation synergistic process 2 Gel layer is transformed into amorphous ZrO 2 A ceramic layer;
step 4, preparing a low surface energy chemical modifier solution, and depositing ZrO on the surface 2 Soaking the filter paper of the ceramic layer in chemical modifier for a period of time, taking out the filter paper, washing and drying to obtain ZrO for high-density solvent oil/water separation 2 /filter paper.
The invention is also characterized in that:
ZrO configured in step 1 2 The concentration of the sol is in the range of 0.1-1.0mol/L.
The filter paper in step 2 should be selected from medium-speed qualitative filter paper or quick-speed qualitative filter paper.
In step 2, the filter paper is coated with ZrO 2 The dipping time in the sol is not less than 1 minute, and the centrifugal speed of the filter paper is500-2000 rpm, centrifuging time of 0.5-2.0 min and drying temperature of 25-80 deg.c. .
In the step 3, the wavelength of an ultraviolet lamp used by a sol-gel method and/or a low-temperature photochemical degradation synergistic process is less than 257.3nm, and the photon energy is greater than 472KJ/mol; the irradiation time is 15-60 minutes, the synchronous heating equipment is a heating table, and the heating temperature is 80-150 ℃.
For ZrO in step 4 2 The solute of the chemical modifier solution used for nonpolar chemical modification of the amorphous ceramic coating is octadecyltrimethoxysilane (C) 18 ) Hexadecyltrimethoxysilane (C) 16 ) N-sunflower-base trimethoxysilane (C) 10 ) Methoxytrimethoxysilane (C) 1 ) The solvent is absolute ethyl alcohol, and the mass concentration of the chemical modifier is 0.5% -2.0%.
The dipping process in the step 4 is to deposit ZrO on the surface at the room temperature of 25 DEG C 2 Soaking the filter paper of the ceramic layer in the chemical modifier for more than 12 hours; washing with absolute ethyl alcohol after chemical modification, and finally drying at the room temperature of 25-100 ℃.
The beneficial effects of the invention are as follows: the invention relates to ZrO for high-density solvent oil/water separation 2 The preparation method of the filter paper solves the problems of poor recycling performance and poor acid and alkali resistance stability of the filter paper material in oil-water separation in the prior art. The sol-gel method and the photochemical reaction method are combined by adopting the sol-gel method/low-temperature photochemical degradation synergistic process, and ZrO can be realized under the low-temperature condition 2 The ceramic layer is deposited on the inflammable filter paper substrate, and then the common filter paper is endowed with superhydrophobicity/superlipophilicity and excellent oil-water separation performance through simple chemical modification; zrO for high-density solvent oil/water separation 2 The filter paper material has simple preparation process and low cost, and can meet the requirement of industrialized mass production; at the same time ZrO 2 The ceramic layer has stable chemical property and good bonding force with filter paper substrate, and can endow ZrO in oil-water separation application 2 Excellent recyclability and acid/base resistance of the filter paper.
Drawings
FIG. 1 is a schematic illustration of one embodiment of the present inventionZrO for high-density solvent oil/water separation 2 ZrO on the surface of Filter paper in the preparation method of Filter paper 2 X-ray diffraction pattern of ceramic layer;
FIG. 2 shows a ZrO for high-density solvent oil/water separation according to the present invention 2 ZrO for separating high-density solvent oil/water by distilled water droplets and chlorobenzene droplets in preparation method of filter paper 2 Graph of wettability effect on filter paper;
FIG. 3 shows a ZrO for high-density solvent oil/water separation according to the present invention 2 ZrO for high-density solvent oil/water separation in preparation method of filter paper 2 Graph of separation effect of filter paper on chlorobenzene/distilled water mixed solution.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The invention relates to ZrO for high-density solvent oil/water separation 2 The preparation method of the filter paper comprises the following steps:
step 1, preparing ZrO 2 Sol;
ZrO configured in step 1 2 The concentration of the sol is in the range of 0.1-1.0mol/L.
Step 2, soaking the filter paper with clean surface in the prepared ZrO at room temperature 2 In the sol, taking out the filter paper, centrifuging and drying, and depositing a layer of ZrO on the surface of the filter paper 2 Gel;
the filter paper in step 2 should be selected from medium-speed qualitative filter paper or quick-speed qualitative filter paper.
In step 2, the filter paper is coated with ZrO 2 The dipping time in the sol is not less than 1 minute, the centrifugation speed of the filter paper is 500-2000 revolutions per minute, the centrifugation time is 0.5-2.0 minutes, and the drying treatment temperature is 25-80 ℃ at room temperature.
Step 3, coating ZrO on the surface of the filter paper by adopting a sol-gel method/low-temperature photochemical degradation synergistic process 2 Gel layer is transformed into amorphous ZrO 2 A ceramic layer;
in the step 3, the wavelength of an ultraviolet lamp used by a sol-gel method and/or a low-temperature photochemical degradation synergistic process is less than 257.3nm, and the photon energy is greater than 472KJ/mol; the irradiation time is 15-60 minutes, the synchronous heating equipment is a heating table, and the heating temperature is 80-150 ℃.
Step 4, preparing a low surface energy chemical modifier solution, and depositing ZrO on the surface 2 The filter paper of the ceramic layer is immersed in the chemical modifier for a period of time, and the filter paper is washed and dried after being taken out, so that the super-hydrophobic/super-oleophilic characteristics of the ZrO 2/filter paper are endowed. Obtaining ZrO for separating high-density solvent oil/water 2 /filter paper.
For ZrO in step 4 2 The solute of the chemical modifier solution used for nonpolar chemical modification of the amorphous ceramic coating is octadecyltrimethoxysilane (C) 18 ) Hexadecyltrimethoxysilane (C) 16 ) N-sunflower-base trimethoxysilane (C) 10 ) Methoxytrimethoxysilane (C) 1 ) The solvent is absolute ethyl alcohol, and the mass concentration of the chemical modifier is 0.5% -2.0%.
The dipping process in the step 4 is to deposit ZrO on the surface at the room temperature of 25 DEG C 2 Soaking the filter paper of the ceramic layer in the chemical modifier for more than 12 hours; washing with absolute ethyl alcohol after chemical modification, and finally drying at the room temperature of 25-100 ℃.
The invention relates to ZrO for high-density solvent oil/water separation 2 ZrO prepared by preparation method of filter paper 2 The filter paper has super-hydrophobic/super-oleophylic characteristics and has excellent separation effect on the high-density solvent oil/water mixed solution. The water can be pure water or corrosive acidic water, alkaline water, brine, etc., and the high-density solvent oil can be one or more of chlorobenzene, dichloromethane, 1, 2-dichloroethane and chloroform. ZrO produced 2 The filter paper oil-water separation material has excellent oil-water separation efficiency, and the separation efficiency of the filter paper oil-water separation material for a plurality of high-density solvent oils/water can reach more than 97 percent
The invention relates to ZrO for high-density solvent oil/water separation 2 ZrO prepared by preparation method of filter paper 2 The filter paper has excellent circulation stability, and the separation efficiency of the filter paper on various high-density oil/water is still kept above 94% after continuous oil-water separation work for more than 100 hours.
The invention relates to a high-density solventZrO for oil/water separation 2 The preparation method of the filter paper comprises the steps of preparing amorphous ZrO on the surface of the filter paper 2 Ceramic layer, then re-facing ZrO 2 The ceramic layer is subjected to nonpolar chemical modification to endow the filter paper with superhydrophobicity/superhydrophilicity, so that the filter paper has a function of separating a high-density solvent oil/water mixed solution. Taking into account ZrO 2 The ceramic layer has excellent durability, acid/alkali corrosion resistance and wear resistance, and the ZrO for high-density solvent oil/water separation 2 The preparation method of the filter paper adopts a sol-gel method/low-temperature photochemical degradation synergistic process to firstly deposit a layer of amorphous ZrO2 ceramic layer on the filter paper, and then uses a surface self-assembly technology to coat ZrO on the surface of the filter paper 2 The ceramic layer is subjected to nonpolar chemical modification so as to endow the filter paper with superhydrophobic/superhydrophilic properties. Compared with the traditional method of preparing nano particles and then fixing the nano particles on the surface of filter paper, the method overcomes the technical problems of poor recycling property and poor acid/alkali resistance of the oil-water separation filter paper material.
Example 1
Firstly, 20ml of absolute ethyl alcohol is taken as a solvent, 0.2g of acetylacetone is weighed and dissolved in the absolute ethyl alcohol, the sol is stirred for 30 minutes at room temperature, 0.77g of zirconium n-butoxide is added into the sol after the stirring is finished, the stirring is continued for 4 hours at room temperature, and 0.2ml of acetic acid is dripped into the sol in the stirring process. Standing and aging for 12 hours after stirring is finished to obtain ZrO with concentration of 0.1mol/L 2 And (3) sol.
The quick qualitative filter paper with clean surface is soaked in the sol for 1 min, so that the pores of the filter paper are fully soaked in the sol. Centrifuging the filter paper at 500 rpm for 0.5 min after soaking, naturally airing at room temperature of 25deg.C, and coating a layer of ZrO on the surface of the filter paper 2 A gel layer. ZrO (ZrO) 2 The filter paper of the gel layer is placed on a heating table at 80 ℃ and simultaneously is irradiated with ultraviolet light with the wavelength of 257.3nm for 15 minutes to lead the ZrO 2 Gel layer conversion to ZrO 2 And a ceramic layer. FIG. 1 shows ZrO on the surface of filter paper 2 Ceramic layer X-ray diffraction pattern as shown in fig. 1: x-ray diffraction peak position and ZrO 2 The standard PDF card has consistent peak positions but diffraction peaksSteamed bread shape, indicating ZrO 2 The ceramic layer exhibits an amorphous state. Finally, zrO is coated 2 The filter paper of the ceramic layer was impregnated with 0.5 mass% octadecyltrimethoxysilane (C 18 ) And (3) naturally airing the filter paper at room temperature of 25 ℃ after soaking in the solution for 12 hours, wherein the filter paper has super-hydrophobic/super-oleophilic performance after drying. FIG. 2 shows distilled water droplets and chlorobenzene droplets in ZrO 2 A photograph of wettability on filter paper, as shown in FIG. 2, shows that chlorobenzene colored with dye is completely immersed in filter paper, and distilled water droplets colored with dye are repelled into a sphere, indicating ZrO after chemical modification 2 The filter paper has excellent super-hydrophobicity/super-lipophilicity. ZrO after measured chemical modification 2 The static contact angle of distilled water on the surface of the filter paper is 155 DEG, and the static contact angle of chlorobenzene is 0 deg. FIG. 3 is a photograph showing the separation process of a ZrO 2/filter paper p-chlorobenzene/distilled water mixed solution after chemical modification, wherein the upper layer liquid is distilled water, and the lower layer liquid is chlorobenzene. ZrO after chemical modification 2 The filter paper only allows chlorobenzene to pass through, while distilled water is repelled. ZrO after chemical modification 2 The separation efficiency of the filter paper on the chlorobenzene/distilled water mixed solution is 99.4 percent. After continuous oil-water separation work for more than 100 hours, the separation efficiency of the p-chlorobenzene/distilled water is still kept at 97.5 percent.
Example 2
Firstly, 20ml of absolute ethyl alcohol is taken as a solvent, 0.6g of acetylacetone is weighed and dissolved in the absolute ethyl alcohol, the sol is stirred for 45 minutes at room temperature, 2.3g of zirconium n-butoxide is added into the sol after the stirring is finished, the stirring is carried out for 5 hours at room temperature, and 0.4ml of acetic acid is dripped into the sol in the stirring process. And standing and aging for 12 hours after stirring is finished, so that ZrO2 sol with the concentration of 0.3mol/L can be obtained.
The quick qualitative filter paper with clean surface is soaked in the sol for 1.5 minutes, so that the pores of the filter paper are fully soaked in the sol. After the soaking is finished, the filter paper is centrifuged at 1000 rpm for 0.5 min and then dried at 50 ℃, and then a ZrO2 gel layer is coated on the surface of the filter paper. ZrO (ZrO) 2 The filter paper of the gel layer is placed on a heating table at 100 ℃ and simultaneously the filter paper is irradiated by ultraviolet light with the wavelength of 186nm for 30 minutes to obtain ZrO 2 Gel transformation intoZrO 2 A ceramic layer, finally, zrO-coated at room temperature of 25 DEG C 2 The filter paper of the ceramic layer was impregnated with 1.0% by mass of hexadecyltrimethoxysilane (C 16 ) After soaking in the solution for 14 hours, the filter paper was dried at 50 ℃. ZrO after chemical modification 2 The static contact angle of the surface of the filter paper to 1M NaOH aqueous solution is 152 degrees, the static contact angle to chloroform is 0 degree, and excellent super-hydrophobic/super-oleophilic properties are shown. The aqueous solution of chloroform/NaOH was prepared by using 1M aqueous NaOH solution as the aqueous phase and chloroform as the oil phase. ZrO after chemical modification 2 The separation efficiency of the filter paper on the chloroform/NaOH aqueous solution mixture was 97.8%. After continuous oil-water separation work for more than 100 hours, the oil-water separation efficiency of chloroform/NaOH aqueous solution is still kept at 95%.
Example 3
Firstly, 20ml of absolute ethyl alcohol is taken as a solvent, 1.2g of acetylacetone is weighed and dissolved in the absolute ethyl alcohol, the sol is stirred for 60 minutes at room temperature, 4.6g of zirconium n-butoxide is added into the sol after the stirring is finished, the stirring is carried out for 6 hours at room temperature, and 0.6ml of acetic acid is dripped into the sol in the stirring process. Standing and aging for 12 hours after stirring is finished to obtain ZrO with concentration of 0.6mol/L 2 And (3) sol.
The quick qualitative filter paper with clean surface is soaked in the sol for 2 minutes, so that the pores of the filter paper are fully soaked in the sol. Centrifuging the filter paper at 1500 rpm for 0.5 min after soaking, and drying at 60deg.C to obtain a layer of ZrO coating on the surface of the filter paper 2 A gel layer. ZrO (ZrO) 2 Placing the filter paper of the gel layer on a 120 ℃ heating table, and simultaneously carrying out irradiation treatment on the filter paper for 45 minutes by utilizing ultraviolet light with the wavelength of 257.3nm to obtain ZrO 2 Gel to ZrO 2 A ceramic layer, finally to be coated with ZrO 2 The filter paper of the ceramic layer is immersed in 1.5% by mass of n-sunflower-base trimethoxysilane (C 10 ) After soaking in the solution for 16 hours, the filter paper was dried at 60 ℃. ZrO after chemical modification 2 The static contact angles of 1M NaCl aqueous solution on the surface of the filter paper are 151 DEG and the static contact angle of methylene dichloride is 0 deg. With 1M NaCl aqueous solution as water phaseAnd preparing a dichloromethane/NaCl water solution mixed solution by taking dichloromethane as an oil phase. ZrO after chemical modification 2/ The separation efficiency of the filter paper on the dichloromethane/NaCl aqueous solution mixed solution is 97.3%. After continuous operation for more than 100 hours, the separation efficiency of the mixed solution of dichloromethane/NaCl aqueous solution is still kept at 94.8 percent
Example 4
Firstly, 20ml of absolute ethyl alcohol is taken as a solvent, 2g of acetylacetone is weighed and dissolved in the absolute ethyl alcohol, the sol is stirred for 75 minutes at room temperature, 7.67g of zirconium n-butoxide is added into the sol after the stirring is finished, the stirring is carried out for 7 hours at room temperature, and 0.8ml of acetic acid is dripped into the sol in the stirring process. Standing and aging for 12 hours after stirring is finished to obtain ZrO with concentration of 1mol/L 2 And (3) sol.
The quick qualitative filter paper with clean surface is soaked in the sol for 2.5 minutes, so that the pores of the filter paper are fully soaked in the sol. Centrifuging the filter paper at 2000 rpm for 2 min after soaking, and drying at 80deg.C to coat a layer of ZrO on the surface of the filter paper 2 A gel layer. Will be coated with ZrO 2 The filter paper of the gel layer is placed on a heating table at 150 ℃ and simultaneously is irradiated with ultraviolet light with the wavelength of 257.3nm for 60 minutes to obtain ZrO 2 Gel to ZrO 2 A ceramic layer, finally to be coated with ZrO 2 The filter paper of the ceramic layer was impregnated with 2.0% by mass of methoxytrimethoxysilane (C 1 ) And (3) placing the filter paper in the solution for more than 18 hours, and drying the filter paper at 100 ℃ after soaking. ZrO after chemical modification 2 The static contact angle of the 1MHCl aqueous solution on the surface of the filter paper was 151 DEG, and the static contact angle of 1.2-dichloroethane was 0 deg. Preparing a 1.2-dichloroethane/HCl aqueous solution mixed solution by taking a 1M HCl aqueous solution as a water phase and taking 1.2-dichloroethane as an oil phase, and chemically modifying ZrO 2 The separation efficiency of the filter paper on the 1.2-dichloroethane/HCl aqueous solution mixture was 97.1%. The separation efficiency of the 1.2-dichloroethane/HCl aqueous solution is still kept at 94.2% after more than 100 hours of continuous operation.
The invention relates to ZrO for high-density solvent oil/water separation 2 The principle of the preparation method of the filter paper is that the filter paper is coated by dippingPreparing ZrO2 gel layer on the surface, adopting sol-gel method/low temperature photochemical degradation synergistic process, removing organic matters in the ZrO2 gel layer by photochemical degradation reaction, and converting the ZrO2 gel layer into amorphous ZrO2 ceramic layer. Because a large amount of chemical hydroxyl groups are arranged on the surface of the ZrO2 ceramic layer, the surface of the ZrO2 ceramic layer is modified by a nonpolar long-chain alkyl chemical modifier through a molecular self-assembly technology, so that the super-hydrophobic/super-oleophylic property of the ceramic layer is endowed. The superhydrophobic/superoleophilic properties can make filter papers exhibit diametrically opposed wettabilities to high density solvent oils and water. Under the action of gravity, the functionalized ZrO 2/filter paper only allows the high-density solvent oil to pass through for the high-density solvent oil/water mixed solution, so that the functionalized ZrO 2/filter paper shows excellent oil-water separation performance.
The invention relates to ZrO for high-density solvent oil/water separation 2 The preparation method of the filter paper solves the problem of poor recycling performance of the filter paper material in oil-water separation in the prior art. The sol-gel method and the photochemical reaction method are combined by adopting the sol-gel method/low-temperature photochemical degradation synergistic process, and ZrO can be realized under the low-temperature condition 2 The ceramic layer is deposited on the inflammable filter paper substrate, and then the common filter paper is endowed with superhydrophobicity/superlipophilicity and excellent oil-water separation performance through simple chemical modification; zrO for high-density solvent oil/water separation 2 The filter paper material has simple preparation process and low cost, and can meet the requirement of industrialized mass production; at the same time ZrO 2 The ceramic layer has stable chemical property and good bonding force with filter paper substrate, and can endow ZrO in oil-water separation application 2 Excellent recyclability and acid/base resistance of the filter paper.
Claims (2)
1. ZrO for high-density solvent oil/water separation 2 The preparation method of the filter paper is characterized by comprising the following steps:
step 1, preparing ZrO 2 Sol;
formulated ZrO 2 The concentration range of the sol is 0.1-1.0mol/L;
step 2, soaking the filter paper with clean surface in the prepared ZrO at room temperature 2 Taking out filter paper from solAfter centrifugal and drying treatment, depositing a layer of ZrO on the surface of the filter paper 2 Gel;
filter paper on ZrO 2 The dipping time in the sol is not less than 1 minute, the centrifugation speed of the filter paper is 500-2000 revolutions per minute, the centrifugation time is 0.5-2.0 minutes, and the drying treatment temperature is 25-80 ℃;
step 3, coating ZrO on the surface of the filter paper by adopting a sol-gel method/low-temperature photochemical degradation synergistic process 2 Gel layer is transformed into amorphous ZrO 2 A ceramic layer;
the wavelength of an ultraviolet lamp used by a sol-gel method/low-temperature photochemical degradation synergistic process is less than 257.3nm, and photon energy is more than 472KJ/mol; the irradiation time is 15-60 minutes, the synchronous heating equipment is a heating table, and the heating temperature is 80-150 ℃;
step 4, preparing a low surface energy chemical modifier solution, and depositing ZrO on the surface 2 Soaking the filter paper of the ceramic layer in chemical modifier for a period of time, taking out the filter paper, washing and drying to obtain ZrO for high-density solvent oil/water separation 2 A filter paper;
the dipping process in the step 4 is to deposit ZrO on the surface at 25 DEG C 2 Soaking the filter paper of the ceramic layer in the chemical modifier for more than 12 hours; washing with absolute ethyl alcohol after chemical modification, and finally drying at 25-100 ℃;
ZrO for high-density solvent oil/water separation 2 The high-density solvent oil separated by the filter paper is one or a mixture of more of chlorobenzene, dichloromethane, 1, 2-dichloroethane and chloroform, and the water is acidic water, alkaline water or brine with corrosiveness;
the solute of the chemical modifier solution is any one of octadecyl trimethoxy silane, hexadecyl trimethoxy silane, n-sunflower trimethoxy silane and methoxy trimethoxy silane, the solvent is absolute ethyl alcohol, and the mass concentration of the chemical modifier is 0.5% -2.0%.
2. The ZrO for high-density solvent oil/water separation as claimed in claim 1 2 A method for preparing filter paper, characterized in that the filter paper in the step 2 shouldMedium speed qualitative filter paper or fast qualitative filter paper is selected.
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| WO2018069528A1 (en) * | 2016-10-14 | 2018-04-19 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Method for sol-gel coating of textile materials |
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| CN101098998B (en) * | 2004-11-24 | 2010-05-12 | 日本板硝子株式会社 | Inorganic fiber paper |
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