CN114259982A - Zinc oxide silicon-based pillared illite-montmorillonite clay composite material and preparation method and application thereof - Google Patents
Zinc oxide silicon-based pillared illite-montmorillonite clay composite material and preparation method and application thereof Download PDFInfo
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- CN114259982A CN114259982A CN202111672243.6A CN202111672243A CN114259982A CN 114259982 A CN114259982 A CN 114259982A CN 202111672243 A CN202111672243 A CN 202111672243A CN 114259982 A CN114259982 A CN 114259982A
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- 239000002131 composite material Substances 0.000 title claims abstract description 41
- AKVPCIASSWRYTN-UHFFFAOYSA-N zinc oxygen(2-) silicon(4+) Chemical compound [Si+4].[O-2].[Zn+2].[O-2].[O-2] AKVPCIASSWRYTN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 44
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000004927 clay Substances 0.000 claims abstract description 42
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims abstract description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052900 illite Inorganic materials 0.000 claims abstract description 38
- 239000010703 silicon Substances 0.000 claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 38
- 229910021647 smectite Inorganic materials 0.000 claims abstract description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 239000011787 zinc oxide Substances 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012153 distilled water Substances 0.000 claims abstract description 20
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 18
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- -1 sodium modified illite Chemical class 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 13
- 239000003463 adsorbent Substances 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000002351 wastewater Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000011148 porous material Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- IJRVLVIFMRWJRQ-UHFFFAOYSA-N nitric acid zinc Chemical compound [Zn].O[N+]([O-])=O IJRVLVIFMRWJRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 238000012799 strong cation exchange Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a zinc oxide silicon-based pillared illite-montmorillonite clay composite adsorbing material, which comprises the following components in percentage by weight: zinc oxide and silicon-based pillared illite-montmorillonite clay. The preparation method of the zinc oxide silicon-based pillared illite-montmorillonite clay composite adsorption material comprises the following steps: step one, mixing and stirring illite smectite clay, sodium carbonate and distilled water to obtain a sodium modified illite smectite clay suspension; step two, mixing absolute ethyl alcohol, hydrochloric acid and tetraethyl silicate and aging to obtain a silicon-based pillaring agent; thirdly, dropwise adding a silicon-based pillaring agent into the sodium-modified illite-montmorillonite clay suspension to obtain silicon-based pillared illite-montmorillonite clay; and step four, mixing distilled water and ethylenediamine, adding the silicon-based pillared illite-montmorillonite clay, zinc nitrate and sodium hydroxide, stirring and performing ultrasonic treatment to obtain the zinc oxide silicon-based pillillite-montmorillonite clay composite adsorbing material. According to the invention, the silicon-based pillared illite-montmorillonite clay and the zinc oxide are crosslinked, so that the problem of low adsorption capacity on rhodamine B when the illite-montmorillonite clay or the zinc oxide is singly used is avoided, and the adsorption capacity of the adsorption material is improved.
Description
Technical Field
The invention relates to the technical field of wastewater treatment. More specifically, the invention relates to a zinc oxide silicon-based pillared illite-montmorillonite clay composite material as well as a preparation method and application thereof.
Background
Water pollution is a serious challenge facing today's world. How to economically and environmentally treat pollutants (such as organic dyes) which are difficult to degrade in wastewater has become a hot point of research for scientists. Rhodamine B (RhB) is a synthetic organic heteroanthracene dye, and is widely applied to the industries of textile, paint, leather, paper making and the like. However, rhodamine B as a triphenylmethane derivative has good water solubility, is easy to analyze and strong in representativeness, has very high toxicity to organisms caused by directly discharging water, and is suspected to be a carcinogen due to rat experiments. Rhodamine B is not only harmful to the environment but also poses potential threats to people, animals and plants, and therefore, the pollution of harmful dyes in wastewater is urgently removed. At present, a plurality of waste water treatment methods exist, wherein an adsorption method is an economic, efficient and relatively environment-friendly repairing method and is one of the most common waste water treatment technologies.
The previous common methods for removing rhodamine B in wastewater include chemical method, electrolytic method, biological method, membrane separation and the like, in the method for removing rhodamine, because layered hydrous silicate minerals formed by illite smectite clay (I/S) ultrafine particles have better adsorbability, the illite clay has the advantages of low cost, rich reserves, strong cation exchange capacity and environmental protection, and is widely used for wastewater treatment. However, the illite smectite clay has very limited adsorption capacity, and the effect of removing rhodamine B in wastewater is influenced.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.
The invention also aims to provide a zinc oxide silicon-based pillared illite-montmorillonite clay composite material, which avoids the problem of low adsorption capacity to rhodamine B when illite-montmorillonite clay or zinc oxide is singly used by crosslinking silicon-based pillillite-montmorillonite clay and zinc oxide, and improves the adsorption capacity of an adsorption material.
Still another object of the present invention is to provide a method for preparing a zinc oxide silicon-based pillared illite-montmorillonite clay composite material.
Still another purpose of the invention is to provide an application of the zinc oxide silicon-based pillared illite-montmorillonite clay composite material in removing rhodamine B in wastewater.
To achieve these objects and other advantages in accordance with the purpose of the invention, there is provided a composite adsorbent material of illite montmorillonite clay based on zinc oxide silicon, comprising: zinc oxide and silicon-based pillared illite-montmorillonite clay.
The invention also provides a preparation method of the zinc oxide silicon-based pillared illite-montmorillonite clay composite adsorbing material, which comprises the following steps of:
step one, mixing and stirring illite smectite clay, sodium carbonate and distilled water to obtain a sodium modified illite smectite clay suspension;
step two, mixing absolute ethyl alcohol, hydrochloric acid and tetraethyl silicate and aging to obtain a silicon-based pillaring agent;
thirdly, dropwise adding a silicon-based pillared agent into the sodium-modified illite-montmorillonite clay suspension, continuously stirring for 3 hours after dropwise adding, aging, filtering, and sequentially drying, calcining and crushing a filtrate to obtain silicon-based pillared illite-montmorillonite clay;
and step four, mixing distilled water and ethylenediamine, adding silicon-based pillared illite clay, zinc nitrate and sodium hydroxide, stirring, performing ultrasonic treatment, heating at 200 ℃, filtering, drying the precipitate, calcining, and crushing to obtain the zinc oxide silicon-based pillillite clay composite adsorbing material.
Preferably, in the step one, the dosage ratio of the illite smectite clay to the sodium carbonate to the distilled water is 1g:0.5g:50 mL; in the second step, the dosage ratio of illite smectite clay, tetraethyl silicate, hydrochloric acid and absolute ethyl alcohol is 1g to 5.6mL to 0.6mL to 0.8mL, and the mass fraction of the hydrochloric acid is 16%; in the fourth step, the dosage ratio of the silicon-based pillared illite to the zinc nitrate to the sodium hydroxide to the ethylenediamine to the distilled water is 1g to 1.5g to 0.5g to 60mL to 25 mL.
Preferably, in the third step, the filtrate is washed 3 times with deionized water and absolute ethyl alcohol in sequence, and then dried and calcined.
Preferably, in the third step, the silicon-based pillaring agent is added dropwise into the sodium-modified illite smectite clay suspension at a rate of 1 mL/min.
Preferably, in the third step, the filtrate is dried and calcined under the following conditions: 500 ℃, the time is 3h, and the heating rate is 2 ℃/min.
Preferably, in the fourth step, the condition for calcining the precipitate is as follows: the temperature is 450 ℃, the time is 3h, and the heating rate is 2 ℃/min.
Preferably, the temperature for drying the filtrate in the third step is 60 ℃ and the drying time is 12h, and the temperature for drying the precipitate in the fourth step is 60 ℃ and the drying time is 24 h.
The invention also provides an application of the zinc oxide silicon-based pillared illite-montmorillonite clay composite material, and an application of the zinc oxide silicon-based pillillite-montmorillonite clay composite adsorption material in removing rhodamine B in wastewater.
The invention at least comprises the following beneficial effects:
firstly, the invention avoids the problem of low adsorption capacity to rhodamine B when the illite-montmorillonite clay or zinc oxide is singly used by crosslinking the silicon-based pillared illite-montmorillonite clay and the zinc oxide, and improves the adsorption capacity of the adsorption material.
Secondly, the invention prepares a silicon-based pillaring agent by adopting tetraethyl silicate, carries out inorganic modification on illite-montmorillonite clay, and then prepares the zinc oxide/silicon pillared illite-montmorillonite clay composite adsorbing material by adopting a method of firstly hydrothermal and then calcining, so that the interlayer structure of the illite-montmorillonite clay is expanded and supported, the adsorption capacity of the illite-montmorillonite clay on rhodamine B is further improved, and the illite-montmorillonite clay composite adsorbing material has better using effect.
Thirdly, the invention has the advantages of wide raw material distribution, low price, high cation exchange capacity, simple preparation process, shortened production time, easy control of preparation process, high production efficiency, small environmental pollution, capability of greatly reducing industrial cost and higher industrial utilization value.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is an XRD diagram of a zinc oxide/silica-based pillared illite smectite clay composite adsorbing material according to one embodiment of the present invention;
FIG. 2 is a diagram showing the effect of the zinc oxide/silicon-based pillared illite-montmorillonite clay composite adsorbing material on rhodamine B according to one technical scheme of the invention.
Detailed Description
The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
The Shangsi Illite/montmorillonite clay (I/S) is a mineral for transition from montmorillonite to Illite, a rare and high-quality mineral resource newly found by Wendend science and technology companies in Shangxi province, is a great finding after bentonite, kaolin, Illite clay, attapulgite clay and the like, and is known as 'king of thousands of earth and ten thousands of earth' by experts, and is a rare and precious nonmetal silicate layered clay mineral in the world. The mineral resources consist of natural micro-nano particles, and the illite smectite clay mineral is detected to be 120 square kilometers, 140 meters thick and nearly 300 hundred million tons in the world of the former thinking. Illite clay generally appears in reservoirs with shallow burial depths, strong water sensitivity of montmorillonite is determined due to strong hydrophilicity and high cation exchange capacity of montmorillonite, and illite can take various forms, grows in a bridging mode in pores, is distributed in a staggered mode, is easy to block pore throats, and reduces reservoir permeability. The illite smectite clay is in a honeycomb shape, a semi-honeycomb shape, a cotton-like shape and the like after being expanded.
< example 1>
A zinc oxide silicon-based pillared illite-montmorillonite clay composite adsorption material comprises: zinc oxide and silicon-based pillared illite-montmorillonite clay.
The illite smectite clay in this example was obtained from Guangxi defense harbor City, Male building materials Co., Ltd. the clay was formed by stacking silica tetrahedron and alumina octahedron in 1:1 and 2:1 type with-OH, Al between layers3+、K+、Na+Plasma; the specific surface area, average pore diameter, total pore volume and the sum of the pore diameters are respectively 40.9m2/g、11.4nm、0.1166cm3(ii) in terms of/g. The water in this example is distilled water, and all other drug specifications used in this example are analytical grade.
< example 2>
A zinc oxide silicon-based pillared illite-montmorillonite clay composite adsorption material comprises: zinc oxide and silicon-based pillared illite-montmorillonite clay.
The preparation method of the zinc oxide silicon-based pillared illite-montmorillonite clay composite adsorption material comprises the following steps:
step one, mixing illite-montmorillonite clay, sodium carbonate and distilled water at room temperature and stirring for 24 hours to obtain a sodium-modified illite-montmorillonite clay suspension;
step two, mixing absolute ethyl alcohol, hydrochloric acid (the mass fraction is 16%) and tetraethyl silicate, and sealing and aging for 1h at room temperature to obtain a silicon-based pillaring agent;
dropwise adding a silicon-based pillaring agent into the sodium-modified illite smectite clay suspension (a constant-pressure dropping funnel is adopted for dropwise adding) at the temperature of 50 ℃ under the stirring condition, continuously stirring for 3 hours after the dropwise adding is finished, standing and aging for 24 hours, filtering to obtain a filtrate, and sequentially drying, calcining (calcining in a muffle furnace) and crushing (grinding) the filtrate to obtain silicon-based pillared illite smectite clay;
step four, (mixing distilled water and ethylenediamine, and then carrying out silica-based pillared illite clay and nitric acidZinc and sodium hydroxide) distilled water and ethylenediamine are mixed and added with silica-based pillared illite clay and zinc nitrate (Zn (NO)3)2·6H2O) and sodium hydroxide are stirred for 30min, ultrasonic treatment is carried out for 20min at room temperature, the mixture is heated (high-pressure reaction kettle) for 12h at 200 ℃, filtration is carried out to obtain precipitate, the precipitate is sequentially washed with absolute ethyl alcohol for three times and distilled water for three times, and the precipitate is dried, calcined and crushed (ground) to obtain the zinc oxide silicon-based pillared illite smectite composite adsorbing material.
In the first step, the dosage ratio of illite smectite clay, sodium carbonate and distilled water is 1g:0.5g:50 mL; in the second step, the dosage ratio of illite smectite clay, tetraethyl silicate, hydrochloric acid and absolute ethyl alcohol is 1g to 5.6mL to 0.6mL to 0.8mL, and the mass fraction of the hydrochloric acid is 16%; in the fourth step, the dosage ratio of the silicon-based pillared illite to the zinc nitrate to the sodium hydroxide to the ethylenediamine to the distilled water is 1g to 1.5g to 0.5g to 60mL to 25 mL.
In the third step, the filtrate is washed 3 times with deionized water and absolute ethyl alcohol in sequence (firstly, the filtrate is washed three times with deionized water and then washed three times with absolute ethyl alcohol), and then dried and calcined.
In the third step, the silicon-based pillaring agent is added dropwise into the sodium-modified illite smectite clay suspension at the rate of 1 mL/min.
In the third step, the filtered substance is dried and calcined under the following conditions: 500 ℃, the time is 3h, and the heating rate is 2 ℃/min.
In the fourth step, the condition for calcining the precipitate is as follows: the temperature is 450 ℃, the time is 3h, and the heating rate is 2 ℃/min.
In the third step, the temperature for drying the filtered substances is 60 ℃, and the drying time is 12 hours, and in the fourth step, the temperature for drying the precipitates is 60 ℃, and the drying time is 24 hours.
The application of the zinc oxide silicon-based pillared illite-montmorillonite clay composite material and the application of the zinc oxide silicon-based pillared illite-montmorillonite clay composite adsorption material in removing rhodamine B in wastewater.
The illite smectite clay in this example was obtained from Guangxi defense harbor City, Male building materials Co., Ltd, and the clay was piled in 1:1 and 2:1 forms from silicon-oxygen tetrahedra and aluminum-oxygen octahedraStacked with-OH and Al between layers3+、K+、Na+Plasma; the specific surface area, average pore diameter, total pore volume and the sum of the pore diameters are respectively 40.9m2/g、11.4nm、0.1166cm3(ii) in terms of/g. The water in this example is distilled water, and all other drug specifications used in this example are analytical grade.
The adsorbent obtained in example 2 (silica-based pillared illite montmorillonite clay composite adsorbent) was named ZnO/Si- (I/S).
< comparative example 1>
Illite clay from the same source as in example 2 was used as the adsorbent material (designated (I/S)).
< comparative example 2>
An adsorbent material was prepared by the method of example 2, except that step four was not performed in this comparative example, namely: firstly, obtaining sodium-modified illite-montmorillonite clay suspension through the first step, obtaining a silicon-based pillaring agent through the second step, then dropwise adding the silicon-based pillaring agent into the sodium-modified illite-montmorillonite clay suspension, continuously stirring for 3 hours after dropwise adding, aging, filtering, and sequentially drying, calcining and crushing a filtered substance to obtain silicon-based pillared illite-montmorillonite clay (namely an adsorbing material, namely Si- (I/S)).
< comparative example 3>
An adsorbent material was prepared by the method of example 2, except that step three was not performed in this comparative example, namely: firstly obtaining sodium modified illite smectite clay suspension in the first step, obtaining a silicon-based pillaring agent in the second step, mixing distilled water and ethylenediamine in the fourth step, adding zinc nitrate and sodium hydroxide, stirring, performing ultrasonic treatment, heating at 200 ℃, filtering, drying, calcining and crushing a precipitate to obtain the zinc oxide illite smectite clay composite adsorbing material (named as ZnO/(I/S)).
< comparative example 4>
An adsorbent material was prepared by the method of example 2, except that the operations of step one, step two, and step three were not performed in this comparative example, that is: mixing distilled water and ethylenediamine, adding zinc nitrate and sodium hydroxide, stirring, performing ultrasonic treatment, heating at 200 deg.C, filtering, drying the precipitate, calcining, and pulverizing to obtain zinc oxide adsorbing material (named as ZnO).
< Experimental characterization >
1. Structural parameters of the adsorbent Material
Preparing five groups of adsorbing materials by adopting the methods of the embodiment 2 and the comparative examples 1-4, and respectively detecting the specific surface area, the pore volume and the average pore diameter of the five groups of adsorbing materials, wherein the detection results are shown in table 1;
table 1 shows the structural parameters of five groups of adsorbents
| Group of | Specific surface area m2/g | Pore volume cm3/g | Average pore diameter nm |
| Comparative example 1 | 40.9 | 0.1166 | 11.4 |
| Comparative example 2 | 106.7 | 0.2451 | 9.2 |
| Comparative example 4 | 25.3 | 0.2343 | 37.1 |
| Comparative example 3 | 17.2 | 0.0898 | 20.7 |
| Example 2 | 26.8 | 0.1450 | 21.6 |
Comparing and analyzing the examples and the comparative examples 1 to 4, it can be seen that the structural parameters of the specific surface area, the pore volume and the average pore diameter of the zinc oxide silicon-based pillared composite adsorbing material obtained in the example 2 are in the middle, but the adsorption performance of the example 2 is the best, which indicates that the adsorption mechanism is not physical adsorption, but chemical adsorption of the composite material to the dye, the dye molecules and the adsorbent of the example 2 are subjected to chemical reaction to form firm adsorption chemical bonds and surface complexes, and the dye molecules can not move freely on the surface.
2. XRD spectrogram
Preparing five groups of adsorbing materials by adopting the methods of the example 2 and the comparative examples 1-4, and respectively measuring XRD spectrograms as shown in figure 1;
according to fig. 1, it can be seen that the characteristic peak of the modified illite smectite clay still exists, but the peak position is narrow, and the illite smectite clay is processed to form a new characteristic peak.
3. Adsorption effect of adsorption material on rhodamine B
Preparing five groups of adsorbing materials by adopting the methods of the embodiment 2 and the comparative examples 1-4, and respectively adsorbing rhodamine B, wherein the concentration of the rhodamine B in the detected wastewater is 20mg/L, the using amount of the adsorbing materials is 0.5g/L, and the detection result is shown in figure 2;
from fig. 2, it can be seen that the removal rate of the composite adsorbing material of illite-montmorillonite clay based on silica-based pillared columns reaches 92% within 50 min.
The number of apparatuses and the scale of the process described herein are intended to simplify the description of the present invention. The application, modification and variation of the zinc oxide silicon-based pillared illite-montmorillonite clay composite adsorbing material, the preparation method and the application thereof are obvious to those skilled in the art.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the embodiments shown and described without departing from the generic concept as defined by the claims and their equivalents.
Claims (9)
1. The zinc oxide silicon-based pillared illite-montmorillonite clay composite adsorbing material is characterized by comprising the following components in percentage by weight: zinc oxide and silicon-based pillared illite-montmorillonite clay.
2. The preparation method of the zinc oxide-silicon-based pillared illite-montmorillonite clay composite adsorbing material as claimed in claim 1, which comprises the following steps:
step one, mixing and stirring illite smectite clay, sodium carbonate and distilled water to obtain a sodium modified illite smectite clay suspension;
step two, mixing absolute ethyl alcohol, hydrochloric acid and tetraethyl silicate and aging to obtain a silicon-based pillaring agent;
thirdly, dropwise adding a silicon-based pillared agent into the sodium-modified illite-montmorillonite clay suspension, continuously stirring for 3 hours after dropwise adding, aging, filtering, and sequentially drying, calcining and crushing a filtrate to obtain silicon-based pillared illite-montmorillonite clay;
and step four, mixing distilled water and ethylenediamine, adding silicon-based pillared illite clay, zinc nitrate and sodium hydroxide, stirring, performing ultrasonic treatment, heating at 200 ℃, filtering, drying the precipitate, calcining, and crushing to obtain the zinc oxide silicon-based pillillite clay composite adsorbing material.
3. The preparation method of the illite smectite clay composite adsorbing material based on zinc oxide silicon, according to claim 2, wherein in the step one, the illite smectite clay, the sodium carbonate and the distilled water are used in a ratio of 1g:0.5g:50 mL; in the second step, the dosage ratio of illite smectite clay, tetraethyl silicate, hydrochloric acid and absolute ethyl alcohol is 1g to 5.6mL to 0.6mL to 0.8mL, and the mass fraction of the hydrochloric acid is 16%; in the fourth step, the dosage ratio of the silicon-based pillared illite to the zinc nitrate to the sodium hydroxide to the ethylenediamine to the distilled water is 1g to 1.5g to 0.5g to 60mL to 25 mL.
4. The preparation method of the composite adsorbing material of the zinc oxide-silicon-based pillared illite-montmorillonite clay as claimed in claim 2, wherein in the third step, the filtered substance is sequentially washed with deionized water and absolute ethyl alcohol for 3 times, then dried and calcined.
5. The method for preparing the illite smectite clay composite adsorbing material based on zinc oxide silicon based pillared, according to claim 2, wherein in the third step, the silicon based pillaring agent is added dropwise into the sodium modified illite smectite clay suspension at a rate of 1 mL/min.
6. The preparation method of the zinc oxide-silicon-based pillared illite-montmorillonite clay composite adsorbing material as claimed in claim 2, wherein in the third step, the filtered substance is dried and calcined under the following calcining conditions: 500 ℃, the time is 3h, and the heating rate is 2 ℃/min.
7. The method for preparing a composite adsorbent according to claim 2, wherein in the fourth step, the condition for calcining the precipitate is: the temperature is 450 ℃, the time is 3h, and the heating rate is 2 ℃/min.
8. The method for preparing the composite adsorbent according to claim 2, wherein the temperature for drying the filtrate in the third step is 60 ℃ and the drying time is 12 hours, and the temperature for drying the precipitate in the fourth step is 60 ℃ and the drying time is 24 hours.
9. The application of the ZnO silicon-based pillared illite-montmorillonite clay composite material obtained by the preparation method according to any one of claims 3 to 8, wherein the ZnO silicon-based pillillite-montmorillonite clay composite adsorption material is applied to removing rhodamine B in wastewater.
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