CN110201644B - A kind of modified montmorillonite, its preparation method and application - Google Patents
A kind of modified montmorillonite, its preparation method and application Download PDFInfo
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class 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 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims abstract description 38
- 229940012189 methyl orange Drugs 0.000 claims abstract description 38
- 238000001179 sorption measurement Methods 0.000 claims abstract description 37
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 35
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 21
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 21
- 239000011734 sodium Substances 0.000 claims abstract description 21
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 11
- 239000002351 wastewater Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- -1 dioctadecyl tetrahydroxyethyl dibromopropane diammonium Chemical compound 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000005341 cation exchange Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 abstract description 11
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 125000002091 cationic group Chemical group 0.000 abstract description 4
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 125000001165 hydrophobic group Chemical group 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000000975 dye Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910017059 organic montmorillonite Inorganic materials 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 239000000979 synthetic dye Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- LPLKJLLIRPEGHK-UHFFFAOYSA-N 2,2-dihydroxyethyl-methyl-octadecylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[NH+](C)CC(O)O LPLKJLLIRPEGHK-UHFFFAOYSA-N 0.000 description 1
- 229910018512 Al—OH Inorganic materials 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000010919 dye waste Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000012799 strong cation exchange Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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Abstract
本发明涉及一种改性蒙脱土、其制备方法及其应用。本发明改性蒙脱土的制备方法通过双十八烷基四羟乙基二溴丙二铵对钠基蒙脱土进行微波改性处理制得层间距更大的改性蒙脱土，为有机污染物提供了更多的吸附空间，同时由于改性蒙脱土引入了双十八烷基四羟乙基二溴丙二铵的疏水基团和阳离子基团，而使其疏水性增强，表面带正电荷，与阴离子污染物之间存在相互吸引的静电作用，从而使改性蒙脱土能有效去除废水中的有机污染物，特别是甲基橙，改性蒙脱土对甲基橙的吸附量可高达200mg/g以上。
The present invention relates to a modified montmorillonite, its preparation method and its application. In the preparation method of the modified montmorillonite of the present invention, the sodium-based montmorillonite is subjected to microwave modification treatment by dioctadecyltetrahydroxyethyldibromopropanediammonium to obtain the modified montmorillonite with a larger interlayer spacing, which is: Organic pollutants provide more adsorption space, and at the same time, the hydrophobicity of modified montmorillonite is enhanced due to the introduction of hydrophobic groups and cationic groups of dioctadecyltetrahydroxyethyldibromopropanediammonium. The surface is positively charged, and there is an electrostatic attraction between the anionic pollutants, so that the modified montmorillonite can effectively remove the organic pollutants in the wastewater, especially the methyl orange. The adsorption capacity can be as high as 200mg/g or more.
Description
Technical Field
The invention belongs to the field of solid materials and the field of water treatment, and relates to modified montmorillonite, a preparation method and application thereof.
Background
Most of the dyes currently used in industry are synthetic dyes containing large amounts of toxic, non-biodegradable organic compounds. Once discharged into the natural environment, untreated dye wastewater can pose a serious environmental pollution challenge and even threaten human life. Therefore, the development of the technology for treating organic matters in synthetic dye wastewater has received extensive attention from researchers. Methyl Orange (MO) is a water-soluble azo compound, which is a representative dye, often present in dye waste water. There are many methods for treating dye wastewater, among which the adsorption method is an economical, efficient, relatively environmentally friendly remediation method, and is one of the most commonly used wastewater treatment techniques.
Montmorillonite is widely used in wastewater treatment because of its low cost, abundant reserves, strong cation exchange capacity and environmental protection. Although montmorillonite has an adsorption ability, this ability is limited and its adsorption property must be improved by an appropriate method. The surfactant can be absorbed on the surface of the montmorillonite or inserted between layers of the montmorillonite through a cation exchange reaction with the montmorillonite, so that the surface of the montmorillonite is changed, the interlayer spacing is increased, the original hydrophilicity is changed into lipophilicity, and the affinity of the montmorillonite to the dye is further increased.
To date, most researchers have been devoted to modifying montmorillonites with traditional single-chain surfactants, and few studies and reports have been made with gemini surfactants, particularly those containing hydroxyl groups in the alkyl chain. Compared with the traditional quaternary ammonium compounds, the gemini quaternary ammonium salts are an emerging class of cationic surfactants, each gemini quaternary ammonium salt molecule has two head groups with positive charges, so that excellent properties such as good synergistic effect, lower Krafft point, improved wetting and foaming performance, better solubilizing capability and surface activity are endowed, and the adsorption behavior of the gemini quaternary ammonium salts is also obviously influenced. However, according to the research results, the adsorption capacity of montmorillonite modified by gemini quaternary ammonium salt to methyl orange is still foundRelatively low, such as Bo Liu et al (B.Liu, X.Wang, B.Yang, R.Sun, Rapid modification of montmorillonite with novel cationic surfactants and Materials adsorption for methyl orange, Materials Chemistry&Physics,2011,130 (3): 1220-1226.) Gemini quaternary ammonium surfactant 18-3-18 (C)43H92N2Cl2And the molecular weight is 707), the organic montmorillonite is prepared by microwave radiation for 1h, the interlayer spacing of the prepared organic montmorillonite (18-3-18-Mt) is only 2.31nm at most, and the maximum adsorption quantity to methyl orange is only about 50 mg/g.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide modified montmorillonite, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
in a first aspect, the invention provides a preparation method of modified montmorillonite, which comprises the following steps: dispersing sodium montmorillonite (Na-Mt) in water, slowly adding Dioctadecyl Tetrahydroxyethyl Dibromopropane Diammonium (DTDD) water solution to obtain suspension, then placing the suspension in a microwave reactor, setting microwave power, reaction temperature and reaction time, collecting precipitate after the reaction is finished, and then washing the precipitate with water until the washed solution and AgNO are mixed3And (3) detecting no bromide ion in the solution reaction, and then drying the washed precipitate to obtain a dried precipitate, namely the modified montmorillonite (DMt).
The structural formula of DTDD is shown below:
after the sodium montmorillonite is subjected to DTDD microwave modification treatment, the interlayer spacing is increased, more adsorption spaces are provided for organic pollutants, and meanwhile, the hydrophobicity of the sodium montmorillonite is enhanced due to the introduction of a hydrophobic group of DTDD; because the cationic group of DTDD is introduced, the surface of the DTDD carries positive charges, and the DTDD and anionic pollutants have electrostatic interaction of mutual attraction, so that the prepared modified montmorillonite can effectively remove organic pollutants in wastewater.
As a preferred embodiment of the preparation method, the dosage of the dioctadecyl tetrahydroxyethyl dibromopropane diammonium is more than 0.5 times of the cation exchange capacity of the sodium-based montmorillonite; as a more preferable embodiment of the preparation method, the dosage of the dioctadecyl tetrahydroxyethyl dibromopropane diammonium is 1.0 to 1.5 times of the cation exchange capacity of the sodium-based montmorillonite. When the dosage of DTDD is more than 0.5 times of the cation exchange capacity of the sodium-based montmorillonite, the interlamellar spacing of the modified montmorillonite is increased to more than 1.96nm from the original 1.24 +/-0.1 nm after the sodium-based montmorillonite is modified, and particularly when the dosage of DTDD is 1.0-1.5 times of the cation exchange capacity of the sodium-based montmorillonite, the interlamellar spacing of the modified montmorillonite reaches 4.09 +/-0.1 nm, so that a larger adsorption space can be provided for organic pollutants, more DTDD groups are introduced, and the adsorption capacity of the modified montmorillonite on the organic pollutants is stronger.
As a preferred embodiment of the preparation method, the microwave power is 800W, the reaction temperature is 85 ℃, and the reaction time is 1 h.
As a preferable embodiment of the preparation method of the present invention, the ratio of sodium montmorillonite to total water in the raw materials for the reaction is 1g:37.5 mL.
As a preferred embodiment of the preparation method of the present invention, the sodium montmorillonite is directly used for preparing the modified montmorillonite without purification treatment after purchase. The sodium-based montmorillonite is directly used for microwave modification without treatment after purchase, the interlamellar spacing of the prepared modified montmorillonite can be obviously improved and can reach 4.09 +/-0.1 nm, and the adsorption capacity to methyl orange can be obviously improved to more than 200 mg/g.
In a second aspect, the invention provides modified montmorillonite prepared by the preparation method.
In a third aspect, the invention also provides application of the modified montmorillonite prepared by the preparation method in removing organic pollutants in wastewater.
As a preferred embodiment of the use of the present invention, the organic contaminants comprise methyl orange; as a more preferable embodiment of the application of the invention, the adsorption capacity of the modified montmorillonite to methyl orange is more than 200 mg/g; as a further preferable embodiment of the application of the invention, the adsorption quantity of the modified montmorillonite to methyl orange is 249.42 mg/g. Under the same adsorption condition, the maximum adsorption quantity of 18-3-18-Mt to methyl orange is only about 50mg/g, while the adsorption quantity of the modified montmorillonite (DMt) to methyl orange can reach 99.81 mg/g; the adsorption capacity can reach 200mg/g or even 249.42mg/g by changing the adsorption condition, which is probably partly due to DMt introduced hydroxyl in DTDD to generate hydrogen bond interaction with methyl orange.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the preparation method of the modified montmorillonite of the invention carries out microwave modification treatment on sodium-based montmorillonite through dioctadecyl tetrahydroxy ethyl dibromopropane diammonium to prepare the modified montmorillonite with larger interlayer spacing, provides more adsorption space for organic pollutants, and simultaneously leads the hydrophobicity of the modified montmorillonite to be enhanced because the modified montmorillonite introduces hydrophobic groups and cationic groups of the dioctadecyl tetrahydroxy ethyl dibromopropane diammonium, the surface of the modified montmorillonite is provided with positive charges, and the modified montmorillonite has electrostatic interaction of mutual attraction with anionic pollutants, thereby leading the modified montmorillonite to be capable of effectively removing the organic pollutants in wastewater.
(2) The modified montmorillonite prepared by the preparation method of the modified montmorillonite can be used for removing organic pollutants in wastewater, particularly methyl orange, and the adsorption capacity can reach more than 200 mg/g.
Drawings
FIG. 1 is a diagram of the synthesis and adsorption mechanism of modified montmorillonite (DMt) according to the present invention;
FIG. 2 is an infrared spectrum of Na-montmorillonite and the modified montmorillonite of examples 1-3;
FIG. 3 is an X-ray diffraction pattern of sodium-based montmorillonite and the modified montmorillonite of examples 1-3;
FIG. 4 is a graph showing the adsorption effect of sodium-based montmorillonite and the modified montmorillonite of example 2 and comparative example 1 on methyl orange.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
One embodiment of the preparation method of the modified montmorillonite comprises the following steps: firstly, dissolving dioctadecyl tetrahydroxyethyl dibromopropane diammonium into 80mL of water to obtain a dioctadecyl tetrahydroxyethyl dibromopropane diammonium water solution; dispersing 4.0g of sodium montmorillonite which is purchased from the market into 70mL of water directly without treatment, slowly adding aqueous solution of dioctadecyl tetrahydroxyethyl dibromopropane diammonium to obtain suspension, then placing the suspension into a microwave reactor, setting the microwave power to be 800W, the reaction temperature to be 85 ℃, the reaction time to be 1h, collecting precipitate by centrifugation after the reaction is finished, and washing the precipitate by water until the washed solution and AgNO are washed3The solution reaction does not detect bromide ions, then freeze-drying the cleaned precipitate at-40 ℃, and then grinding and screening by a 65-mesh screen to obtain powder with the particle size of below 65 meshes, namely the modified montmorillonite; wherein the dosage of the dioctadecyl tetrahydroxyethyl dibromopropane diammonium is 0.5 times of the cation exchange capacity of the sodium montmorillonite (namely 0.5 CEC).
Example 2
One embodiment of the method of the present invention for preparing modified montmorillonite; the preparation method is the same as that of the example 1 except that the dosage of the dioctadecyl tetrahydroxyethyl dibromopropane diammonium is 1.0 time of the cation exchange capacity of the sodium-based montmorillonite (namely 1.0 CEC).
Example 3
One embodiment of the method of the present invention for preparing modified montmorillonite; the preparation method is the same as that of the example 1 except that the dosage of the dioctadecyl tetrahydroxyethyl dibromopropane diammonium is 1.5 times of the cation exchange capacity of the sodium-based montmorillonite (namely 1.5 CEC).
Comparative example 1
Comparative example 1 is a method of preparing modified montmorillonite; the preparation method is the same as the embodiment 2 except that the modifier is single-chain surfactant octadecyl methyl dihydroxyethyl ammonium bromide (namely OMDAB), and the prepared modified montmorillonite is marked as OMt; the structural formula of OMDAB is shown below:
the applicant carried out the following tests to illustrate the effect of the present application:
(1) infrared Spectrum testing
The applicants conducted IR spectroscopy on Na-montmorillonite (Na-Mt) and the modified montmorillonite of examples 1-3, and the results are shown in FIG. 2.
As can be seen from FIG. 2, the Na-montmorillonite and the modified montmorillonite of examples 1-3 have several common infrared absorption peaks, for example, 1037cm-1At 528cm of Si-O bending vibration peak-1The peak of Al-O-Si bending vibration at, and 463cm-1-1The peak of the Si-O-Si bending vibration. In addition, 3636cm-1The band of (A) corresponds to-OH stretching vibration of Al-OH and Si-OH groups in sodium-based montmorillonite, and is 3325cm-1Broadband sum of (A) 1634cm-1The wider bands of (A) are respectively attributed to stretching and deformation vibration of interlayer water molecules HOH in the sodium-based montmorillonite. Compared with sodium-based montmorillonite, the modified montmorillonite is 2917cm-1And 2852cm-1Two new bands appear, which are the asymmetric and symmetric extensional oscillation peaks of-CH in the surfactant during intercalation, and 1468cm-1The band at (a) corresponds to bending vibration of the-CH bond in the in-plane surfactant. In addition, compared with sodium-based montmorillonite, the modified montmorillonite sample is 3325cm-1And 1634cm-1The peak of the O — H bond at (a) is weakened, indicating that water molecules in the interlayer of the sodium-based montmorillonite are replaced by surfactant, indicating that insertion or adsorption into the sodium-based montmorillonite has been successful.
(2) XRD test
The applicant carried out XRD tests on sodium montmorillonite (Na-Mt) and the modified montmorillonite of examples 1-3, and the specific results are shown in FIG. 3.
In fig. 3, the d001 diffraction peak of sodium montmorillonite appears at 7.138 ° and the corresponding interlayer distance is calculated to be 1.24 ± 0.1nm according to the bragg equation (n λ 2dsin θ). Unlike Na-Mt, the d001 peak of the modified montmorillonite is shifted to a lower 2 θ value, indicating that extension of the interlayer space has occurred and is a surfactant that is embedded due to microwave irradiation. With the increase of the DTDD dosage, the interlayer spacing of the modified montmorillonite is remarkably increased from 1.24 +/-0.1 nm to 4.09 +/-0.1 nm, which shows that the interlayer spacing of the modified montmorillonite is positively correlated with the DTDD dosage.
(3) Adsorption experiment of methyl orange
The applicant added 40mg of the modified montmorillonite of example 2 to 100mL of 20mg/L, 40mg/L, 60mg/L, 80mg/L, 100mg/L and 120mg/L of Methyl Orange (MO) dye, respectively, sealed with a sealing cap, placed in a constant temperature water bath (room temperature) and stirred at 400rpm for 2 hours, and then rapidly taken the adsorbed solution and passed through a 0.45 μm hydrophilic Polyethersulfone (PES) syringe filter, and then measured the MO concentration with an ultraviolet-visible spectrophotometer, and the results of the MO adsorption amount and removal rate are shown in Table 1.
TABLE 1 MO adsorption amount and removal rate test results
As can be seen from table 1, the amount of MO removed by DMt increased with increasing MO concentration; when the initial concentration of MO was increased from 20mg/L to 120mg/L, the amount of adsorbed MO increased from 49.94mg/g to 249.42mg/g, and the MO removal efficiency decreased from 99.87% to 83.14%, but a high removal rate remained. This phenomenon may be related to an increase in the competition of MO molecules for the available space on the DMt surface, and may also be related to an increase in steric hindrance caused by adsorption of other molecules to nearby adsorption sites. At lower concentrations, DMt has more binding sites not occupied by MO molecules and therefore provides a relatively high removal rate. However, as the concentration of MO increases, DMt tends to saturate at the active sites, and when the concentration of MO exceeds 80mg/L, the removal efficiency of MO decreases rapidly, but the amount of adsorbed MO continues to increase, probably due to the formation of a second layer of adsorbate.
In addition, the applicant also compares the methyl orange adsorption effect of the modified montmorillonite in the example 2 with that of the sodium-based montmorillonite and that of the modified montmorillonite in the comparative example 1, and the specific method is the same as the methyl orange adsorption experiment except that the methyl orange concentration is 40 mg/L. As can be seen from fig. 4, the color of the methyl orange solution after OMt adsorption was lighter than Na-Mt, while the color of the methyl orange solution after DMt adsorption was lighter than OMt and colorless; DMt the adsorption capacity of methyl orange is much higher than that of Na-Mt and OMt, which shows that the gemini surfactant is more beneficial to the improvement of montmorillonite adsorption performance than the traditional single-chain surfactant.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of modified montmorillonite is characterized by comprising the following steps: the preparation method comprises the following steps: dispersing sodium-based montmorillonite in water, slowly adding a dioctadecyl tetrahydroxyethyl dibromopropane diammonium water solution to obtain a suspension, then placing the suspension in a microwave reactor, setting microwave power, reaction temperature and reaction time, collecting precipitates after the reaction is finished, and then washing the precipitates with water until the washed solution and AgNO are mixed3And (3) the solution reaction does not detect bromide ions, and then drying the washed precipitate to obtain a dried precipitate, namely the modified montmorillonite.
2. The method of claim 1, wherein: the dosage of the dioctadecyl tetrahydroxy ethyl dibromo diammonium is more than 0.5 times of the cation exchange capacity of the sodium montmorillonite.
3. The method of claim 1, wherein: the dosage of the dioctadecyl tetrahydroxyethyl dibromopropane diammonium is 1.0 to 1.5 times of the cation exchange capacity of the sodium-based montmorillonite.
4. The method of claim 1, wherein: the microwave power is 800W, the reaction temperature is 85 ℃, and the reaction time is 1 h.
5. The method of claim 1, wherein: in the raw materials of the reaction, the ratio of the sodium montmorillonite to the total water is 1g:37.5 mL.
6. The method of claim 1, wherein: the sodium montmorillonite is directly used for preparing the modified montmorillonite without purification treatment after purchase.
7. A modified montmorillonite prepared by the preparation method of any one of claims 1-6.
8. The use of a modified montmorillonite prepared by the method of any one of claims 1-6, wherein: the modified montmorillonite is used for removing organic pollutants in wastewater.
9. Use according to claim 8, characterized in that: the organic contaminants include methyl orange.
10. Use according to claim 9, characterized in that: the adsorption quantity of the modified montmorillonite to methyl orange is up to more than 200 mg/g.
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