CN115724438A - High-hydrophobicity organic modified natural zeolite and preparation method thereof - Google Patents
High-hydrophobicity organic modified natural zeolite and preparation method thereof Download PDFInfo
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- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 157
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 239000010457 zeolite Substances 0.000 title claims abstract description 157
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 25
- 238000000227 grinding Methods 0.000 claims abstract description 24
- 238000000967 suction filtration Methods 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 21
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- JCGDCINCKDQXDX-UHFFFAOYSA-N trimethoxy(2-trimethoxysilylethyl)silane Chemical compound CO[Si](OC)(OC)CC[Si](OC)(OC)OC JCGDCINCKDQXDX-UHFFFAOYSA-N 0.000 claims description 13
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 10
- IZRJPHXTEXTLHY-UHFFFAOYSA-N triethoxy(2-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CC[Si](OCC)(OCC)OCC IZRJPHXTEXTLHY-UHFFFAOYSA-N 0.000 claims description 10
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 30
- 239000002994 raw material Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 239000000243 solution Substances 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910001579 aluminosilicate mineral Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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Abstract
The invention discloses a high-hydrophobicity organic modified natural zeolite and a preparation method thereof, wherein the method comprises the following steps: step 1, firstly, mixing the following components in a mass ratio of 1: (0.05-0.2): (20-50) taking natural zeolite, a silane coupling agent containing 6 hydrolyzable groups and monohydric alcohol, preparing the monohydric alcohol into a monohydric alcohol aqueous solution with the concentration of 20-40%, then mixing the natural zeolite, the silane coupling agent I and the monohydric alcohol aqueous solution, fully stirring at 50-80 ℃, and then sequentially carrying out suction filtration, alcohol washing, drying and grinding to obtain the high-hydrophilicity hydroxyl-rich natural zeolite; step 2, mixing the raw materials in a mass ratio of 1: (0.001-0.01): (20-50) mixing the high-hydrophilicity hydroxyl-rich natural zeolite, the silane coupling agent containing the organic hydrophobic chain groups and the nonpolar solvent, fully stirring at 50-80 ℃, and then carrying out suction filtration, water washing, drying and grinding to obtain the high-hydrophobicity organic modified natural zeolite with good hydrophobicity.
Description
Technical Field
The invention relates to modification of natural zeolite, in particular to high-hydrophobicity organic modified natural zeolite and a preparation method thereof.
Background
The natural zeolite is a porous water-containing aluminosilicate mineral, the structure of the natural zeolite is formed by connecting silicon-oxygen tetrahedrons and aluminum-oxygen tetrahedrons through shared oxygen, and the natural zeolite has excellent adsorption, catalysis and ion exchange performances, and has wide application prospects in the aspect of environmental pollutant treatment. The natural zeolite resources in China are very rich, and nearly 400 zeolite deposits (points) are found, and the total reserve is about 30 hundred million tons. The silicon-aluminum ratio of the natural zeolite is 2-6, the natural zeolite belongs to medium-low silicon zeolite, the surface of the natural zeolite contains hydroxyl groups, the hydrophilicity is high, the removal effect of the natural zeolite on hydrophobic pollutants is low, and the wide application of the natural zeolite in the treatment of environmental pollutants is greatly limited. Therefore, how to improve the hydrophobicity of natural zeolite has become one of the topics of great interest to researchers at home and abroad.
The hydrophilicity and hydrophobicity of zeolite are closely related to the hydroxyl content of the zeolite, and the lower the hydroxyl content is, the higher the hydrophobicity of the zeolite is, and conversely, the higher the hydrophilicity is. The organic modification of natural zeolite can effectively reduce the surface hydroxyl content and increase the content of hydrophobic groups, thereby improving the hydrophobicity of the zeolite. However, limited by the hydroxyl content on the surface of the natural zeolite, the solid loading of the organic modifier on the surface is often not high, so that the hydrophobic properties of the obtained organically modified natural zeolite are not good. Therefore, how to increase the hydroxyl content on the surface of natural zeolite, increase the solid loading of organic groups on the surface of zeolite, and further improve the surface hydrophobicity becomes an important issue to be solved urgently.
Disclosure of Invention
The invention aims to provide a high-hydrophobicity organic modified natural zeolite and a preparation method thereof, wherein the synthesis method is simple, the conditions are easy to control, and the organic modified natural zeolite has good hydrophobicity.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of high-hydrophobicity organic modified natural zeolite comprises the following steps:
step 1, preparation of high-hydrophilicity hydroxyl-rich natural zeolite
Firstly, mixing the following components in a mass ratio of 1: (0.05-0.2): (20-50) taking natural zeolite, a silane coupling agent I and monohydric alcohol, adding the monohydric alcohol into deionized water to prepare a monohydric alcohol aqueous solution with the concentration of 20% -40%, then mixing the natural zeolite, the silane coupling agent I and the monohydric alcohol aqueous solution, fully stirring at 50-80 ℃, and then sequentially carrying out suction filtration, alcohol washing, drying and grinding to obtain the high-hydrophilicity hydroxyl-group-enriched natural zeolite;
the silane coupling agent I is a silane coupling agent containing 6 hydrolyzable groups;
step 2, preparation of high-hydrophobicity organic modified natural zeolite
According to the mass ratio of 1: (0.001-0.01): (20-50) mixing the high-hydrophilicity hydroxyl-rich natural zeolite, a silane coupling agent II and a nonpolar solvent, fully stirring at 50-80 ℃, and then carrying out suction filtration, washing, drying and grinding to obtain the high-hydrophobicity organic modified natural zeolite;
the silane coupling agent II is a silane coupling agent with a single molecular structure containing at least one organic hydrophobic chain group.
Further, the silane coupling agent I in the step 1 is 1, 2-bis (triethoxysilyl) ethane or 1, 2-bis (trimethoxysilyl) ethane.
Further, the monohydric alcohol aqueous solution in the step 1 is an ethanol aqueous solution, a methanol aqueous solution or an n-butanol aqueous solution with the concentration of 20-40%.
Further, the silane coupling agent II in the step 2 is mercaptopropyltrimethoxysilane, dodecyltrimethoxysilane or methylphenyldimethoxysilane.
Further, the nonpolar solvent in the step 2 is p-xylene, toluene or benzene.
Furthermore, the stirring time in the step 1 and the step 2 is 12 to 36 hours.
Further, the drying in the step 1 and the step 2 is carried out at the temperature of 60 ℃.
The high hydrophobic organic modified natural zeolite has average critical surface tension of 34-46 mN/m.
The invention has the following beneficial effects:
according to the invention, 6 hydroxyl groups formed by hydrolysis of the silane coupling agent I react with hydroxyl groups on the surface of natural zeolite to form a large number of hydroxyl groups on the surface of the zeolite, and then the hydroxyl groups are reacted with hydroxyl groups formed by hydrolysis of the silane coupling agent II to introduce organic hydrophobic chain groups on the surface of the natural zeolite to the maximum extent.
Drawings
FIG. 1: FTIR spectra of the highly hydrophilic hydroxyl-rich natural zeolite prepared in example 3 of the present invention and natural zeolite;
FIG. 2: FTIR spectra of the high-hydrophobicity organic modified natural zeolite prepared in example 3 of the present invention, the organic modified natural zeolite prepared by a conventional method, and the natural zeolite;
FIG. 3: flotation result curve I of the high-hydrophobicity organic modified natural zeolite prepared in the embodiment 3 of the invention and the organic modified natural zeolite prepared by the conventional method;
FIG. 4: flotation result curve two of the high-hydrophobicity organic modified natural zeolite prepared in the embodiment 3 of the invention and the organic modified natural zeolite prepared by the conventional method;
FIG. 5: the reaction principle in the preparation process of the invention is shown schematically.
Detailed Description
The following examples are given to illustrate the present invention in further detail, but are not intended to limit the scope of the present invention.
Example 1
Step 1, preparation of high-hydrophilicity hydroxyl-rich natural zeolite
Firstly, mixing the following components in a mass ratio of 1:0.05: taking natural zeolite, 1, 2-bis (trimethoxysilyl) ethane and absolute ethyl alcohol, adding the absolute ethyl alcohol into deionized water to prepare an ethanol water solution with the concentration of 20%, then mixing the natural zeolite, the 1, 2-bis (trimethoxysilyl) ethane and the ethanol water solution, stirring for 12 hours at 60 ℃, performing suction filtration, washing for 2 times by using the absolute ethyl alcohol, then drying at 60 ℃, and finally grinding to obtain the high-hydrophilicity natural zeolite rich in hydroxyl, wherein the water vapor adsorption capacity of the high-hydrophilicity natural zeolite is 49mg/g;
step 2, preparation of high-hydrophobicity organic modified natural zeolite
According to the mass ratio of 1:0.001:20, mixing the high-hydrophilicity hydroxyl-rich natural zeolite, dodecyl trimethoxy silane and toluene, stirring for 12 hours at 60 ℃, performing suction filtration, washing for 2 times by using deionized water, drying at 60 ℃, and finally grinding to obtain the high-hydrophobicity organic modified natural zeolite, wherein the average critical surface tension of the high-hydrophobicity organic modified natural zeolite is 46mN/m.
Example 2
Step 1, preparation of high-hydrophilicity hydroxyl-rich natural zeolite
Firstly, mixing the following components in a mass ratio of 1:0.07:25 taking natural zeolite, 1, 2-bis (trimethoxysilyl) ethane and absolute ethyl alcohol, adding the absolute ethyl alcohol into deionized water to prepare an ethanol water solution with the concentration of 30%, then mixing the natural zeolite, the 1, 2-bis (trimethoxysilyl) ethane and the ethanol water solution, stirring for 12 hours at 60 ℃, performing suction filtration, washing for 3 times by using the absolute ethyl alcohol, then drying at 60 ℃, and finally grinding to obtain the high-hydrophilicity natural zeolite rich in hydroxyl groups, wherein the water vapor adsorption capacity of the high-hydrophilicity natural zeolite is 52mg/g;
step 2, preparation of high-hydrophobicity organic modified natural zeolite
According to the mass ratio of 1:0.003:25 mixing the high-hydrophilicity hydroxyl-rich natural zeolite, the dodecyl trimethoxy silane and the toluene, stirring and processing for 12 hours at the temperature of 60 ℃, then carrying out suction filtration, washing for 3 times by using deionized water, then drying at the temperature of 60 ℃, and finally grinding to obtain the high-hydrophobicity organic modified natural zeolite, wherein the average critical surface tension of the high-hydrophobicity organic modified natural zeolite is 44mN/m.
Example 3
Step 1, preparation of high-hydrophilicity hydroxyl-rich natural zeolite
Firstly, mixing the following components in a mass ratio of 1:0.1:30 taking natural zeolite, 1, 2-bis (trimethoxysilyl) ethane and absolute ethyl alcohol, adding the absolute ethyl alcohol into deionized water to prepare 40% aqueous solution of ethyl alcohol, then mixing the natural zeolite, the 1, 2-bis (trimethoxysilyl) ethane and the aqueous solution of ethyl alcohol, stirring for 18 hours at 70 ℃, performing suction filtration, washing for 3 times by using the absolute ethyl alcohol, then drying at 60 ℃, and finally grinding to obtain the highly hydrophilic natural zeolite rich in hydroxyl, wherein the water vapor adsorption capacity of the highly hydrophilic natural zeolite is 54mg/g;
step 2, preparation of high-hydrophobicity organic modified natural zeolite
According to the mass ratio of 1:0.005:30 mixing the high-hydrophilicity hydroxyl-rich natural zeolite, dodecyl trimethoxy silane and toluene, stirring and processing for 18h at 70 ℃, then performing suction filtration, washing for 3 times by using deionized water, then drying at 60 ℃, and finally grinding to obtain the high-hydrophobicity organic modified natural zeolite, wherein the average critical surface tension of the high-hydrophobicity organic modified natural zeolite is 46mN/m.
As can be seen from FIG. 1, the intensity of the Si-OH characteristic peak on the surface of the highly hydrophilic hydroxyl-rich natural zeolite prepared in this example is significantly enhanced, indicating that the natural zeolite chemically reacts with 1, 2-bis (trimethoxysilyl) ethane.
As can be seen from fig. 2, the intensity of the characteristic Si — OH peak on the surface of the high-hydrophobicity organic modified natural zeolite prepared in this example is significantly reduced, indicating that a chemical reaction occurs between the natural zeolite and dodecyltrimethoxysilane.
As can be seen from FIG. 3, the high hydrophobicity organic modified natural zeolite prepared by the method of the present invention still has floating particles at low solution surface tension, which indicates that the sample has good hydrophobicity.
As can be seen from FIG. 4, the average critical surface tension of the high-hydrophobicity organic modified natural zeolite prepared in this example is greater than 71.60mN/m, while the average critical surface tension of the natural zeolite treated by the conventional method is at most 46.20mN/m, which indicates that the hydrophobicity of the natural zeolite is greatly improved by the preparation method of the present invention.
As can be seen from FIG. 5, in the first step of this example, 6 hydroxyl groups formed by hydrolysis of silane coupling agent I react with hydroxyl groups on the surface of natural zeolite, so that a large number of hydroxyl groups are formed on the surface of zeolite, and highly hydrophilic natural zeolite rich in hydroxyl groups is obtained; and in the second step, hydroxyl formed by hydrolyzing the silane coupling agent II reacts with the high-hydrophilicity hydroxyl-rich natural zeolite, and organic hydrophobic chain groups are introduced to the surface of the natural zeolite to the maximum extent so as to obtain the high-hydrophobicity organic modified natural zeolite.
Example 4
Step 1, preparation of high-hydrophilicity hydroxyl-rich natural zeolite
Firstly, mixing the following components in a mass ratio of 1:0.08:35 taking natural zeolite, 1, 2-bis (trimethoxysilyl) ethane and methanol, adding methanol into deionized water to prepare a methanol aqueous solution with the concentration of 30%, then mixing the natural zeolite, the 1, 2-bis (trimethoxysilyl) ethane and the methanol aqueous solution, stirring for 18 hours at 70 ℃, performing suction filtration, washing for 2 times by using absolute ethyl alcohol, then drying at 60 ℃, and finally grinding to obtain the high-hydrophilicity hydroxyl-rich natural zeolite with the water vapor adsorption capacity of 44mg/g;
step 2, preparation of high-hydrophobicity organic modified natural zeolite
According to the mass ratio of 1:0.002:35 mixing the high-hydrophilicity hydroxyl-rich natural zeolite, mercaptopropyltrimethoxysilane and p-xylene, stirring for 18h at 70 ℃, performing suction filtration, washing for 2 times by using deionized water, drying at 60 ℃, and finally grinding to obtain the high-hydrophobicity organic modified natural zeolite, wherein the average critical surface tension of the high-hydrophilicity hydroxyl-rich natural zeolite is 43mN/m.
Example 5
Step 1, preparation of high-hydrophilicity hydroxyl-rich natural zeolite
Firstly, mixing the following components in a mass ratio of 1:0.12: taking natural zeolite, 1, 2-bis (trimethoxysilyl) ethane and absolute ethyl alcohol, adding the absolute ethyl alcohol into deionized water to prepare an ethanol water solution with the concentration of 35%, mixing the natural zeolite, the 1, 2-bis (trimethoxysilyl) ethane and the ethanol water solution, stirring and treating for 24 hours at 80 ℃, performing suction filtration, washing for 3 times by using the absolute ethyl alcohol, drying at 60 ℃, and finally grinding to obtain the highly hydrophilic natural zeolite rich in hydroxyl groups, wherein the water vapor adsorption capacity of the highly hydrophilic natural zeolite is 56mg/g;
step 2, preparation of high-hydrophobicity organic modified natural zeolite
According to the mass ratio of 1:0.004:35 mixing the high-hydrophilicity hydroxyl-rich natural zeolite, mercaptopropyl trimethoxysilane and a p-xylene solution, stirring and treating for 24 hours at the temperature of 80 ℃, then performing suction filtration, then washing for 3 times by using deionized water, then drying at the temperature of 60 ℃, and finally grinding to obtain the high-hydrophobicity organic modified natural zeolite, wherein the average critical surface tension of the high-hydrophilicity hydroxyl-rich natural zeolite is 41mN/m.
Example 6
Step 1, preparation of high-hydrophilicity hydroxyl-rich natural zeolite
Firstly, mixing the following components in a mass ratio of 1:0.13:40 taking natural zeolite, 1, 2-bis (triethoxysilyl) ethane and methanol, adding the methanol into deionized water to prepare a 40% methanol water solution, mixing the natural zeolite, the 1, 2-bis (triethoxysilyl) ethane and the methanol water solution, stirring for 24 hours at 80 ℃, performing suction filtration, washing for 2 times by using absolute ethyl alcohol, drying at 60 ℃, and finally grinding to obtain the high-hydrophilicity hydroxyl-rich natural zeolite with the water vapor adsorption capacity of 54mg/g;
step 2, preparation of high-hydrophobicity organic modified natural zeolite
According to the mass ratio of 1:0.006:40 mixing the high-hydrophilicity hydroxyl-rich natural zeolite, mercaptopropyltrimethoxysilane and p-xylene, stirring for 24 hours at 80 ℃, then carrying out suction filtration, washing for 2 times by using deionized water, then drying at 60 ℃, and finally grinding to obtain the high-hydrophobicity organic modified natural zeolite, wherein the average critical surface tension of the high-hydrophilicity hydroxyl-rich natural zeolite is 40mN/m.
Example 7
Step 1, preparation of high-hydrophilicity hydroxyl-rich natural zeolite
According to the mass ratio of 1:0.15:45 taking natural zeolite, 1, 2-bis (triethoxysilyl) ethane and n-butyl alcohol, adding the n-butyl alcohol into deionized water to prepare a 40% n-butyl alcohol aqueous solution, mixing the natural zeolite, 1, 2-bis (triethoxysilyl) ethane and the n-butyl alcohol aqueous solution, stirring for 24 hours at 50 ℃, performing suction filtration, washing for 2 times by using absolute ethyl alcohol, drying at 60 ℃, and finally grinding to obtain the high-hydrophilicity hydroxyl-rich natural zeolite with the water vapor adsorption capacity of 58mg/g;
step 2, preparation of high-hydrophobicity organic modified natural zeolite
According to the mass ratio of 1:0.008:45 mixing the natural zeolite, the methyl phenyl dimethoxy silane and the benzene, stirring and processing for 24 hours at 50 ℃, then performing suction filtration, washing for 2 times by using deionized water, then drying at 60 ℃, and finally grinding to obtain the high-hydrophobicity organic modified natural zeolite, wherein the average critical surface tension of the high-hydrophobicity organic modified natural zeolite is 35mN/m.
Example 8
Step 1, preparation of high-hydrophilicity hydroxyl-rich natural zeolite
According to the mass ratio of 1:0.18:45 taking natural zeolite, 1, 2-bis (triethoxysilyl) ethane and n-butanol, adding the n-butanol into deionized water to prepare a 20% n-butanol aqueous solution, then mixing the natural zeolite, the 1, 2-bis (triethoxysilyl) ethane and the n-butanol aqueous solution, stirring for 36h at 50 ℃, performing suction filtration, washing for 3 times by using absolute ethyl alcohol, then drying at 60 ℃, and finally grinding to obtain the high-hydrophilicity natural zeolite rich in hydroxyl groups, wherein the water vapor adsorption capacity of the high-hydrophilicity natural zeolite is 57mg/g;
step 2, preparation of high-hydrophobicity organic modified natural zeolite
According to the mass ratio of 1:0.009:45 mixing the natural zeolite, the methyl phenyl dimethoxy silane and the benzene, stirring for 36h at 50 ℃, performing suction filtration, washing for 3 times by using deionized water, drying at 60 ℃, and finally grinding to obtain the high-hydrophobicity organic modified natural zeolite, wherein the average critical surface tension of the high-hydrophobicity organic modified natural zeolite is 38mN/m.
Example 9
Step 1, preparation of high-hydrophilicity hydroxyl-rich natural zeolite
According to the mass ratio of 1:0.2: taking natural zeolite, 1, 2-bis (triethoxysilyl) ethane and n-butanol, adding the n-butanol into deionized water to prepare a n-butanol aqueous solution with the concentration of 30%, then mixing the natural zeolite, the 1, 2-bis (triethoxysilyl) ethane and the n-butanol aqueous solution, stirring at 50 ℃ for 36 hours, performing suction filtration, washing for 2 times by using absolute ethyl alcohol, then drying at 60 ℃, and finally grinding to obtain the high-hydrophilicity natural zeolite rich in hydroxyl groups, wherein the water vapor adsorption capacity of the high-hydrophilicity natural zeolite is 58mg/g;
step 2, preparation of high-hydrophobicity organic modified natural zeolite
According to the mass ratio of 1:0.01:50, mixing natural zeolite, methyl phenyl dimethoxy silane and benzene, stirring and treating at 50 ℃ for 36 hours, performing suction filtration, washing with deionized water for 2 times, drying at 60 ℃, and finally grinding to obtain the high-hydrophobicity organic modified natural zeolite with the average critical surface tension of 34mN/m.
Table 1: compounding ratios and condition tables of examples 1 to 9
Claims (8)
1. A preparation method of high-hydrophobicity organic modified natural zeolite is characterized by comprising the following steps:
step 1, preparation of high-hydrophilicity hydroxyl-rich natural zeolite
Firstly, according to the mass ratio of 1: (0.05-0.2): (20-50) taking natural zeolite, a silane coupling agent I and monohydric alcohol, mixing the natural zeolite, the silane coupling agent I and the monohydric alcohol aqueous solution, fully stirring at 50-80 ℃, and then sequentially performing suction filtration, alcohol washing, drying and grinding to obtain the high-hydrophilicity hydroxyl-rich natural zeolite;
the silane coupling agent I is a silane coupling agent containing 6 hydrolyzable groups;
step 2, preparation of high-hydrophobicity organic modified natural zeolite
According to the mass ratio of 1: (0.001-0.01): (20-50) mixing the high-hydrophilicity hydroxyl-rich natural zeolite, a silane coupling agent II and a nonpolar solvent, fully stirring at 50-80 ℃, and then carrying out suction filtration, washing, drying and grinding to obtain the high-hydrophobicity organic modified natural zeolite;
the silane coupling agent II is a silane coupling agent with a single molecular structure containing at least one organic hydrophobic chain group.
2. The method of claim 1, wherein the silane coupling agent I in step 1 is 1, 2-bis (triethoxysilyl) ethane or 1, 2-bis (trimethoxysilyl) ethane.
3. The method of claim 1, wherein the aqueous solution of monohydric alcohol in step 1 is an aqueous solution of ethanol, methanol or n-butanol at a concentration of 20-40% by mass.
4. The method of claim 1, wherein the silane coupling agent II in step 2 is mercaptopropyltrimethoxysilane, dodecyltrimethoxysilane or methylphenyldimethoxysilane.
5. The method for preparing a highly hydrophobic organically modified natural zeolite according to claim 1, wherein the nonpolar solvent in the step 2 is p-xylene, toluene or benzene.
6. The method for preparing high-hydrophobicity organic modified natural zeolite according to claim 1, wherein the stirring time in step 1 and step 2 is 12-36 h.
7. The method of claim 1, wherein the drying in step 1 and step 2 is performed at a temperature of 60 ℃.
8. A highly hydrophobic organically modified natural zeolite prepared by the method of any one of claims 1 to 7, characterized in that the mean critical surface tension of the highly hydrophobic organically modified natural zeolite is 34mN/m to 46mN/m.
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