CN112007615B - Preparation method and application of composite adsorption material for recovering organic sulfur-containing dye - Google Patents
Preparation method and application of composite adsorption material for recovering organic sulfur-containing dye Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 28
- 125000001741 organic sulfur group Chemical group 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 33
- 239000011593 sulfur Substances 0.000 claims abstract description 33
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 31
- -1 ferrocene selenide Chemical class 0.000 claims abstract description 23
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 21
- 239000000975 dye Substances 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 19
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 239000003463 adsorbent Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
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- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000003795 desorption Methods 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- 239000000356 contaminant Substances 0.000 claims description 4
- 239000000988 sulfur dye Substances 0.000 claims description 4
- 229950003937 tolonium Drugs 0.000 claims description 2
- HNONEKILPDHFOL-UHFFFAOYSA-M tolonium chloride Chemical compound [Cl-].C1=C(C)C(N)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 HNONEKILPDHFOL-UHFFFAOYSA-M 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims 1
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- 238000000034 method Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- 231100000719 pollutant Toxicity 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
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- 238000004566 IR spectroscopy Methods 0.000 description 3
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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- IMWICXCTLULCFP-UHFFFAOYSA-N 3-[n-ethyl-3-methyl-4-[(6-methylsulfonyl-1,3-benzothiazol-2-yl)diazenyl]anilino]propanenitrile Chemical group CC1=CC(N(CCC#N)CC)=CC=C1N=NC1=NC2=CC=C(S(C)(=O)=O)C=C2S1 IMWICXCTLULCFP-UHFFFAOYSA-N 0.000 description 1
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 150000003854 isothiazoles Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NLWBJPPMPLPZIE-UHFFFAOYSA-N methyl 4-(bromomethyl)benzoate Chemical compound COC(=O)C1=CC=C(CBr)C=C1 NLWBJPPMPLPZIE-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 229910052711 selenium Inorganic materials 0.000 description 1
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- 150000004867 thiadiazoles Chemical class 0.000 description 1
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- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
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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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/40—Organic compounds containing sulfur
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- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to the technical field of water pollution treatment, and particularly discloses a preparation method and application of a composite adsorption material for recovering organic sulfur-containing dye. The preparation method of the composite adsorption material comprises the steps of carrying out a first reaction on ferrocene selenide shown as a formula (1) and titanium dioxide to prepare an intermediate; and carrying out a second reaction on the intermediate and the CuI to obtain the compound. The invention provides a novel cuprous cluster-titanium dioxide composite adsorbing material and a preparation method thereof, and the novel cuprous cluster-titanium dioxide composite adsorbing material has the characteristics of low cost, mild reaction conditions and convenient process operation. Meanwhile, experiments for treating sulfur-containing dye wastewater through light control prove that the composite adsorbing material can achieve the aims of environmental friendliness, energy conservation, consumption reduction, time conservation, high efficiency and resource regeneration compared with pure titanium dioxide and activated carbon. The invention of the sulfur-containing dye regeneration green technology provides technical support for the industrial wastewater resource treatment, and has important reference value.
Description
Technical Field
The invention relates to the technical field of water pollution treatment, in particular to a preparation method and application of a composite adsorption material for recovering organic sulfur-containing dye.
Background
With the continuous development of industry, the increasingly prominent water pollution problem seriously affects the economic development while threatening the normal life of people. The dye wastewater is wastewater discharged from textile printing and dyeing factories mainly processing cotton, hemp, chemical fibers and blended products thereof, has the characteristics of high organic pollutant content, deep chromaticity, large alkalinity, large water quality change and the like, and belongs to industrial wastewater which is difficult to treat. At present, the physicochemical/biochemical treatment process is generally adopted in the dye wastewater treatment in China, the effluent quality only reaches the secondary standard in the discharge standard of pollutants for textile dyeing and finishing industry, the discharge standard of the pollutants for textile dyeing and finishing industry is improved along with the continuous deepening of the environmental protection concept, and the increase of the scientific and technological investment is urgently needed to further improve the effluent quality.
With the continuous development and progress of the textile printing and dyeing industry, a large amount of novel artificially synthesized dye, auxiliary agent and surfactant are used, so that the biodegradability of the dye wastewater is greatly reduced. Among them, various organic sulfides such as thiazoles, isothiazoles, thiadiazoles, thiophenes and the like have bright color tones and high molar extinction coefficients, and are excellent in dyeing properties as dyes, and excellent in complex fastnesses such as light fastness, washing fastness, acid and alkali fastness, light fastness and the like. However, these dyes are toxic, corrosive and malodorous, and can cause serious pollution to the environment such as the atmosphere, water and soil, and can greatly affect the normal operation of wastewater treatment equipment. The current situation of treating the sulfur-containing dye wastewater is as follows:
1. the conventional biochemical treatment process is difficult to degrade the pollutants;
2. the applicability of a coagulation method, an adsorption method, a membrane technology, an advanced oxidation method and the like in the physicochemical treatment process to sulfur-containing dye molecules is also generally low, for example, the activated carbon is the most commonly used adsorbent in the adsorption method, although the activated carbon has certain removal capacity to BOD, COD, chromaticity and partial organic matters in water, the regeneration energy consumption of the activated carbon is high, economic benefits are not met for treating low-concentration organic sulfur-containing dye, the adsorption capacity of the regenerated activated carbon is reduced to different degrees, and the industrial wide application is limited;
3. at present, the technology of adopting sunlight and repeatedly using a photocatalyst is gradually popularized, although the energy consumption can be partially reduced, the mode of firstly adsorbing and then carrying out photocatalytic oxidative degradation for treating sulfur-containing dye wastewater has serious secondary pollution. Therefore, the method for treating the organic pollutants with low energy consumption and high benefit is found to become an important direction for treating the dye wastewater at present.
4. Researches find that cuprous ions are easy to form coordinate bonds with sulfur-containing organic matters and can change the coordination environment to release the sulfur-containing organic matters under the stimulation of external conditions. Based on the principle, the copper-based functional material suitable for sulfur-containing organic matters is designed, and a new direction can be developed for the dye wastewater treatment technology.
Therefore, cuprous clusters with metal coordination and visible light response activity are designed and connected to TiO through chemical bonds2The surface is constructed with a composite adsorbing materialThe organic sulfur-containing dye develops a new wastewater treatment technology with low energy consumption and high benefit.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of the prior art and provides a composite adsorbing material for treating organic sulfides in wastewater, which can realize environment friendliness, energy conservation, consumption reduction, time saving, high efficiency and resource regeneration.
The technical problem to be solved by the invention is to provide a preparation method of the composite adsorbing material.
The invention finally aims to solve the technical problem of providing the application of the composite adsorbing material.
The invention idea is as follows: firstly, the bridging unit in ferrocene selenide is utilized to be in contact with substrate TiO2Form stable chemical bonds between the two to realize stable load, and obtain a first-step load intermediate; and (3) constructing a stable and efficient cuprous cluster-titanium dioxide composite adsorbing material in situ with the CuI by using effective coordination sites-Se in the ferrocene selenide on the surface of the intermediate and the CuI. Aiming at organic sulfur-containing dye molecules, methylene blue is specially selected as the template dye, and organic sulfur in the structure of the template dye can be used as a coordination site and is effectively matched with a composite adsorption material.
In order to solve the technical problem, the invention discloses a preparation method of a composite adsorption material, which comprises the steps of carrying out a first reaction on ferrocene selenide shown as a formula (1) and titanium dioxide to prepare an intermediate; carrying out a second reaction on the intermediate and CuI to obtain the intermediate;
in the first reaction, the mole ratio of the ferrocene selenide shown as the formula (1) to the titanium dioxide is 1: 2-4, preferably 1: 3; the first reaction is carried out at 40 ℃ for 24 h.
Preferably, the first reaction is to dissolve the ferrocene selenide shown in the formula (1) in a solvent, fully dissolve the ferrocene selenide by ultrasonic, add titanium dioxide into the solvent, react after fully dispersing by ultrasonic, and centrifugally wash the obtained reaction liquid to obtain a solid, namely an intermediate; wherein the solvent is dichloromethane; the concentration of the ferrocene selenide shown in the formula (1) is 0.004 mmol/mL; the titanium dioxide is P25, Degussa titanium dioxide.
In the second reaction, the molar ratio of CuI to the ferrocene selenide shown in the formula (1) is 1.5-2.5: 1, and preferably 2: 1; the second reaction is carried out for 24 hours at room temperature in the dark.
Preferably, the second reaction is to dissolve the CuI in a solvent, fully perform ultrasonic treatment on the solvent, add a solid intermediate into the solvent, perform reaction, and centrifugally wash the obtained reaction solution to obtain a solid; wherein the solvent is acetonitrile; the concentration of CuI was 0.008 mmol/mL.
The composite adsorbing material prepared by the method is also within the protection scope of the invention.
The application of the composite adsorption material in the recovery of sulfur-containing dye is also within the protection scope of the invention.
The application comprises the steps of putting the composite adsorption material into an aqueous solution containing sulfur dye pollutants for sulfur fixation reaction, wherein the sulfur dye pollutants are immobilized on the composite adsorption material; centrifuging, removing sulfur-containing dye pollutants on the surface of the obtained solid by using a desorption solvent under the drive of a light source, and recovering and enriching.
Wherein the sulfur-containing dye contaminant is any one of methylene blue, toluidine blue and azo sulfur-containing dyes; wherein the azo sulfur-containing dye is selected from disperse red 88, 137, 145, 152, 153, 177, 179, 206, 2B, 338, 339, 340, disperse blue 96, 102, 106, 124, 148, 284, 367, 3RT, R-PC, disperse violet S, disperse brilliant blue 870, and disperse green 9.
Wherein, in the aqueous solution of the sulfur-containing dye pollutant, the concentration of methylene blue is 15-18 mg/L.
The dosage of the composite adsorbing material is 1-2 mg/mL methylene blue aqueous solution.
Wherein the sulfur fixation reaction is (room temperature) reaction for 3 min.
Wherein, the light source is a white light LED with light intensityThe degree is 100mW/cm2。
Wherein the desorption solvent is ethanol.
Wherein the desulfurization reaction time is 5 min.
Has the advantages that: compared with the prior art, the invention has the following advantages:
the invention provides a novel cuprous cluster-titanium dioxide composite adsorbing material and a preparation method thereof, and the novel cuprous cluster-titanium dioxide composite adsorbing material has the characteristics of low cost, mild reaction conditions and convenient process operation. Meanwhile, experiments for treating sulfur-containing dye wastewater through light control prove that the composite adsorbing material can achieve the aims of environmental friendliness, energy conservation, consumption reduction, time conservation, high efficiency and resource regeneration compared with pure titanium dioxide and activated carbon. The invention of the sulfur-containing dye regeneration green technology provides technical support for the industrial wastewater resource treatment, and has important reference value.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a synthetic route of ferrocene selenide FcSe in example 1 of the present invention;
FIG. 2 shows the preparation of ferrocene selenide FcSe in example 1 of the present invention1H-NMR chart;
FIG. 3 shows a TiO composite adsorbent used in example 1 of the present invention2@[Cu2I2(FcSe)2]X-ray energy spectrum of (a);
FIG. 4 shows a TiO composite adsorbent used in example 1 of the present invention2@[Cu2I2(FcSe)2]A Fourier infrared spectrogram of (1);
FIG. 5 shows a composite adsorbent, TiO, in example 1 of the present invention2@[Cu2I2(FcSe)2]High resolution transmission electron microscopy images;
FIG. 6 shows a composite adsorbent, TiO, in example 1 of the present invention2@[Cu2I2(FcSe)2]The solid ultraviolet-visible light diffuse reflectance pattern of (a);
FIG. 7 shows a composite adsorbent, TiO, in example 1 of the present invention2@[Cu2I2(FcSe)2]The recycling performance of the organic sulfur-containing dye is improved.
FIG. 8 shows a TiO composite adsorbent used in example 1 of the present invention2@[Cu2I2(FcSe)2]The sulfur fixing performance of the organic sulfur-containing dye is treated;
FIG. 9 shows a composite adsorbent TiO 1 according to example 1 of the present invention2@[Cu2I2(FcSe)2]Fourier infrared spectrogram after sulfur fixation reaction;
FIG. 10 is a Fourier infrared spectrum of methylene blue before and after resource recovery in an embodiment of the present invention.
Detailed Description
Example 1
(1) Synthesis of ferrocene selenide (FcSe):
a250 mL three-necked flask was evacuated and charged with nitrogen three times, and first, dried absolute ethanol (150mL) was charged and evacuated and charged with nitrogen three times. Ferrocene triselenium (0.264g, 0.5mmol) is weighed and added, after ice bath, NaBH is added4(0.189g, 5 mmol). After reaction for 10min, the room temperature is recovered for 2 h. A THF solution of methyl 4- (bromomethyl) benzoate (1mL, 0.108g, 0.5mmol) was added under nitrogen and reacted at room temperature for 24 h. After the reaction is finished, the mixture is subjected to low-temperature rotary evaporation to obtain a solid mixture, the solid mixture is respectively added with distilled water (25mL) for washing and dichloromethane solution (3X 25mL) for multiple times to extract an organic phase, and the lower organic phase is obtained by using anhydrous MgSO4Drying, suction filtering and rotary steaming. And (3) performing 300-mesh 400-mesh column chromatography purification treatment, eluting and separating by using a mixed solution of mobile phase petroleum ether and ethyl acetate, and performing rotary evaporation on the obtained second-stage product to obtain a light yellow solid intermediate (0.185g, 0.45mmol) with the yield of 90%. Theoretical value of elemental analysis: c55.24%, H4.39%, O13.52%, test values: 55.23% of C, 4.39% of H and 13.53% of O.1H NMR(CDCl3):7.85-6.98(C6H4,d,4H),4.07(C5H4,t,2H),4.01(C5H4,t,2H),3.70(SeCH2Ph,s,2H),1.53(CH3,s,1H)。
Repeatedly vacuumizing and filling nitrogen for three times in a 150mL three-neck flask, and then addingThe treated absolute ethyl alcohol (50mL) is dried, and vacuumizing and nitrogen filling are carried out repeatedly for three times. The intermediate (0.32g, 0.5mmol) obtained in the above synthesis was weighed, added with potassium hydroxide (0.224g, 4mmol), and heated at 60 ℃ for reflux reaction for about 1 h. After the reaction, 30mL of water was added, part of the solvent was removed by low-temperature rotary evaporation, and then a suitable amount of dichloromethane solution was added and the aqueous phase was extracted several times. And (3) dropwise adding 6N hydrochloric acid into the obtained water phase to adjust the pH value of the system to be 2, allowing a large amount of precipitate to appear in the solution, standing, filtering and drying in vacuum to obtain the target product ferrocene selenide (0.260g and 0.43mmol), wherein the yield is 85%, and the synthetic route is shown in figure 1. Theoretical value of elemental analysis: c51.01%, H3.62%, O9.12%, test values: c51.02%, H3.62%, O9.11%.1H NMR(CDCl3):12.76(OH,s,1H)7.87-7.05(C6H4,d,4H),4.12(C5H4,t,2H),4.05(C5H4,t,2H),3.76(SeCH2Ph, d,2H) (fig. 2).
(2) Cuprous cluster and titanium dioxide composite adsorption material TiO2@[Cu2I2(FcSe)2]The preparation of (1): ferrocene selenide FcSe (0.128g, 0.2mmol) was weighed and dissolved in 50mL of dichloromethane. Separately weigh TiO2(0.05g, 0.6mmol) was sonicated for about 30min after addition. Then heating to 40 ℃ for heating reflux reaction for 24h, centrifugally separating the obtained mixed solution, and washing the solid for multiple times by using a dichloromethane solution to remove residues. CuI (0.076g, 0.4mmol) was weighed into about 50mL acetonitrile, and the solid was sonicated in this solution and washed by centrifugation as described above, followed by reaction at room temperature in the dark for 24 h. And after the reaction is finished, obtaining the target product composite adsorbing material by the same operation.
Fig. 3 is obtained by testing a sample through an X-ray energy spectrum, and it is confirmed that the effective constituent elements of the composite adsorbent in this example 1 are Ti, Cu, Fe, I, and Se. Cu was tested by ICP plasma emission spectroscopy: fe molar ratio is 1: 1, and prediction of [ Cu2I2(FcSe)2]Cu in the cluster compound: the molar ratio of Fe was consistent, demonstrating TiO2Surface is [ Cu ]2I2(FcSe)2]A cluster compound. FIG. 4 was obtained by Fourier Infrared Spectroscopy, using potassium bromide as a reference test, demonstrating the stepwise loading of ferrocene selenide FcSe, CuITo TiO2The composite adsorbing material TiO in the embodiment 1 of the invention is obtained on the surface2@[Cu2I2(FcSe)2]. FIG. 5 is obtained through a high-resolution transmission electron microscope test sample, and it is proved that the composite adsorbing material TiO in example 1 of the present invention2@[Cu2I2(FcSe)2]Has a stable core-shell structure. By using solid ultraviolet diffuse reflection spectroscopy and barium sulfate as a reference test sample to obtain fig. 6, it is proved that the composite adsorbing material TiO in example 1 of the present invention2@[Cu2I2(FcSe)2]Compared with pure P25, the material has excellent light absorption performance in the visible light region and photoreaction activity.
(3) Composite adsorbing material TiO2@[Cu2I2(FcSe)2]For resource recovery of sulfur-containing dyes: about 20mL of methylene blue aqueous solution (16mg/L) was added to a glass tube, and TiO, which is a composite functional material prepared as described above, was weighed2@[Cu2I2(FcSe)2]Stirring and reacting at room temperature for 3min after 30mg is added, and then carrying out centrifugal separation to obtain the dye-adsorbing composite adsorbing material.
And adding the solid substance into 20mL of ethanol solution again, performing ultrasonic dispersion, and performing white light illumination reaction for 5 min. Composite adsorbing material TiO obtained by centrifugal separation2@[Cu2I2(FcSe)2]The method can be used for repeated recycling, the structure composition of the desorbed sulfur-containing dye in the solution is consistent with that of a pure dye, and resources can be recycled.
The results show that the composite adsorbent TiO targeted in example 12@[Cu2I2(FcSe)2]The method can realize efficient light-operated sulfur fixation-desulfurization recovery and enrichment on the organic sulfur-containing dye wastewater, and proves that the composite adsorbing material TiO in the embodiment 1 has the advantages that the adsorption rate of organic sulfides in the dye wastewater is 96 percent, namely the adsorption amount reaches 10.18mg of methylene blue/catalyst g, the resource regeneration rate is 81 percent of methylene blue, the adsorption and desorption of the composite adsorbing material is 5 times, the cyclic mass loss rate is below 4 percent, and the experimental data of the 1 st to 5 th cyclic adsorption and desorption are shown in the figure 7 and the table 12@[Cu2I2(FcSe)2]The recycled organic sulfur-containing dye has stable repeated cycle performance. By methyleneThe blue dye adsorption experiment, the measured data and figure 8, the graphical representation and the comparison prove that the composite adsorbing material TiO in the embodiment 1 of the invention2@[Cu2I2(FcSe)2]Has the advantage of quick reaction in the sulfur fixation reaction of the organic sulfur-containing dye. FIG. 9, which is obtained by Fourier infrared spectroscopy using potassium bromide as a reference test sample, demonstrates that the composite adsorbing material TiO in example 1 of the present invention2@[Cu2I2(FcSe)2]The effective adsorption of methylene blue dye in sulfur fixing reaction. Fig. 10 is obtained by fourier infrared spectroscopy using potassium bromide as a reference test sample, and it is proved that methylene blue recovered after the adsorption and desorption reaction in example 1 of the present invention has a composition structure identical to that of a pure product, and can be recycled.
Table 1 five cycles of methylene blue recovery using composite adsorbent material of example 1 of the present invention
The correlation calculation formula:
methylene blue water solution regression line c (w) ═ 0.1794a (w) +0.0173(R2 ═ 0.9955)
Regression line c (e) 0.2312a (e)0.0047(R2 ═ 0.9999) of methylene blue ethanol solution
Wherein: c (0) is the initial methylene blue aqueous solution concentration (mg/L)
c (w) concentration of methylene blue aqueous solution after adsorption (mg/L)
c (e) concentration of methylene blue ethanol solution after desorption (mg/L)
V volume of solution (L)
m composite mass (mg)
Example 2: respectively comparing common adsorbents for resource recovery treatment of organic sulfur-containing dyes:
(1) pure titanium dioxide for resource recovery of organic sulfur-containing dyes: adding about 20mL of methylene blue aqueous solution (16mg/L) into a glass tube, weighing 30mg of pure titanium dioxide, adding the pure titanium dioxide, stirring for reacting for 3min, and after the reaction is finished, performing centrifugal separation to obtain a solid; and adding the solid substance into 20ml of ethanol solution again, performing ultrasonic dispersion, and performing white light illumination reaction for 5 min.
(2) The activated carbon is used for resource recovery of organic sulfur-containing dye: adding about 20mL of methylene blue aqueous solution (16mg/L) into a glass tube, weighing active carbon 30mg, adding, stirring for reaction for 3min, and performing centrifugal separation to obtain a solid after the reaction is finished; and adding the solid substance into 20ml of ethanol solution again, performing ultrasonic dispersion, and performing white light illumination reaction for 5 min.
The results show that the pure titanium dioxide of example 2 has no sulfur fixation-desulfurization performance on organic sulfur-containing dyes; the activated carbon shows excellent adsorption performance, the highest adsorption rate of organic sulfides in the dye wastewater can reach 98 percent (5min), but the desorption rate of the material in the subsequent desulfurization experiment is only 2 percent, so that the composite adsorption material TiO2@[Cu2I2(FcSe)2]The 96 percent adsorption rate and the 81 percent resource regeneration rate are far superior to those of the traditional adsorbent active carbon.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
The invention discloses a composite adsorbing material capable of recycling organic sulfur-containing dye and provides a preparation method thereof. Meanwhile, the invention provides the application of the composite adsorbing material in the treatment of sulfur-containing wastewater, and the light-operated sulfur fixation-desulfurization experiment on organic sulfide dye proves that the composite adsorbing material provided by the invention can effectively recycle resources and reuse light to treat sulfur-containing dye. Meanwhile, experiments prove that the composite adsorbing material provided by the invention is a composite adsorbing material for organic sulfide in light treatment wastewater, which is environment-friendly, energy-saving, consumption-reducing, time-saving, efficient and resource-regenerating. The method has important reference value for treating the organic sulfur-containing dye wastewater.
Claims (8)
1. The application of the composite adsorption material in the recovery of organic sulfur-containing dye is characterized in that the preparation method of the composite adsorption material is to perform a first reaction on ferrocene selenide as shown in formula (1) and titanium dioxide to prepare an intermediate; carrying out a second reaction on the intermediate and CuI to obtain the intermediate;
2. the application of claim 1, wherein in the first reaction, the mole ratio of the ferrocene selenide shown in the formula (1) to the titanium dioxide is 1: 2-4, and the first reaction is carried out at 40 ℃ for 24 hours.
3. The application of claim 1, wherein the first reaction is to dissolve the ferrocene selenide shown in the formula (1) in a solvent, then add titanium dioxide into the solvent, and react to obtain the ferrocene selenide; wherein the solvent is dichloromethane; the concentration of the ferrocene selenide shown in the formula (1) is 0.004 mmol/mL.
4. The use according to claim 1, wherein in the second reaction, the molar ratio of CuI to the ferrocene selenide represented by the formula (1) is 1.5-2.5: 1; the second reaction is carried out for 24 hours at room temperature in the dark.
5. The use according to claim 1, wherein the second reaction is prepared by dissolving CuI in a solvent, adding an intermediate into the solution, and reacting; wherein the solvent is acetonitrile; the concentration of CuI was 0.008 mmol/mL.
6. The use of claim 1, wherein the composite adsorbent material is placed in an aqueous solution containing sulfur dye contaminants to undergo a sulfur fixation reaction, wherein the sulfur dye contaminants are immobilized on the composite adsorbent material; centrifuging, removing sulfur-containing dye on the surface of the obtained solid by using a desorption solvent under the drive of a light source, and recovering and enriching.
7. The use according to claim 6, wherein the sulfur-containing dye contaminant is any one of methylene blue, toluidine blue and azo-based sulfur-containing dyes.
8. The use according to claim 6, wherein the light source is a white LED with a light intensity of 100mW/cm2(ii) a The desorption solvent is ethanol.
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