CN111569835A - Methylene blue adsorbent and preparation method and application thereof - Google Patents
Methylene blue adsorbent and preparation method and application thereof Download PDFInfo
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- 229960000907 methylthioninium chloride Drugs 0.000 title claims abstract description 76
- 239000003463 adsorbent Substances 0.000 title claims abstract description 70
- 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 title claims 12
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920002749 Bacterial cellulose Polymers 0.000 claims abstract description 66
- 239000005016 bacterial cellulose Substances 0.000 claims abstract description 66
- 238000001179 sorption measurement Methods 0.000 claims abstract description 42
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 22
- 238000012986 modification Methods 0.000 claims abstract description 16
- 230000004048 modification Effects 0.000 claims abstract description 16
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 18
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 8
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 claims description 6
- RZUBARUFLYGOGC-MTHOTQAESA-L acid fuchsin Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=C(N)C(C)=CC(C(=C\2C=C(C(=[NH2+])C=C/2)S([O-])(=O)=O)\C=2C=C(C(N)=CC=2)S([O-])(=O)=O)=C1 RZUBARUFLYGOGC-MTHOTQAESA-L 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- XHCCWBJFZUXJBV-UHFFFAOYSA-K trisodium 2-[(2-oxido-5-sulfophenyl)diazenyl]-3,6-disulfonaphthalene-1,8-diolate Chemical compound C1=CC(=C(C=C1S(=O)(=O)O)N=NC2=C(C3=C(C=C(C=C3C=C2S(=O)(=O)O)S(=O)(=O)O)[O-])[O-])[O-].[Na+].[Na+].[Na+] XHCCWBJFZUXJBV-UHFFFAOYSA-K 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 abstract description 67
- 230000000694 effects Effects 0.000 abstract description 9
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- 230000015572 biosynthetic process Effects 0.000 abstract 1
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- 238000000967 suction filtration Methods 0.000 description 13
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- 239000000975 dye Substances 0.000 description 9
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 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
- 229920000742 Cotton Polymers 0.000 description 1
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000000084 colloidal system Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
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- 239000011487 hemp Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 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 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 229920002994 synthetic fiber Polymers 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000013171 zeolitic imidazolate framework-6 Substances 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
- B01J20/22—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
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
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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)
Abstract
The methylene blue adsorbent is obtained by modifying bacterial cellulose loaded with a metal organic framework compound ZIF-67 by sulfonic acid groups with a sulfonic acid group substance at least containing two sulfonic acid groups. The adsorbent takes ZIF-67/bacterial cellulose modified by sulfonic acid groups as an effective component, and the-SO in the adsorbent is modified by sulfonic acid groups of ZIF-67 through a multi-sulfonic acid group substance3 ‑With methylene blue-N+(CH3)2The adsorbent has strong electrostatic effect, greatly improves the adsorption capacity of the adsorbent to methylene blue, and can realize the quick and efficient adsorption of the methylene blue. The adsorptionThe preparation method has the advantages of easy synthesis of the agent, simple sulfonic group modification step, mild reaction conditions, low cost, high reaction yield, high methylene blue adsorption speed, large adsorption capacity and easy realization of industrial production.
Description
Technical Field
The invention relates to a methylene blue adsorbent, and in particular relates to a sulfonic group modified metal organic framework compound ZIF-67 loaded bacterial cellulose as a methylene blue adsorbent, a preparation method thereof and application thereof in rapid and efficient adsorption of methylene blue.
Background
Metal-organic frameworks (MOFs) are novel porous coordination compounds with highly regular network structures formed by Metal ions or Metal clusters and organic ligands through coordination bonds and other weak action modes, and have various characteristics of large specific surface area, small density, designable diversified Framework structures, adjustable and controllable potential pore sizes and the like compared with traditional porous materials (such as zeolite, molecular sieve and the like). Meanwhile, the MOFs have the functional characteristics of both metal and organic ligands, have wide application in the fields of gas storage, separation and purification, catalysis and the like, and are hot spots of research in recent years.
Organic dyes are mainly used for dyeing fibers such as cotton, wool, silk, hemp, rayon, synthetic fibers, paper, leather and the like; it can also be used in plastics, oil and grease, soap candle, aluminium product, ink, pencil, colour photographic material and food industry. Along with the continuous development of industrial technology, the harm of industrial dye wastewater is increasingly prominent, wherein methylene blue is commonly used for processing industrial dyes, and the generated wastewater has strong pollution and great harm to human bodies. At present, the treatment methods of organic dyes in wastewater are also various, and the physical treatment methods comprise a precipitation method and an adsorption method, and the chemical treatment methods comprise a neutralization method, a coagulation method and an oxidation method; the biological method comprises a biological rotating disk, a biological rotating cylinder and a biological contact oxidation method. At present, it has been reported that the supported metal-organic framework material having the largest adsorption amount to methylene blue is Fe3O4HKUST-1 with a maximum adsorption of 1277mg/g [ see: m, Kubo, MicroporousMesoporous Materials, 2019, 280: 227-]However, the adsorbent is not easily separated from the solution. The metal organic framework compound ZIF-67 has also been reported to be useful for methylene blue adsorption in an amount of 19.6mg/g [ see: XD Du. Journal of Colloid and Interface Science. 2017,506: 437-441]The adsorption amount is small.
Disclosure of Invention
The invention aims to provide a methylene blue adsorbent, which loads a metal organic framework compound ZIF-67 on a bacterial cellulose carrier, and then carries out sulfonic group modification, so that the methylene blue is quickly and efficiently adsorbed, and the adsorption capacity of the ZIF-67 on the methylene blue is greatly improved.
The invention also aims to provide a preparation method of the methylene blue adsorbent, which has simple preparation process, and the obtained adsorbent has high adsorption quantity, high adsorption speed and good selectivity on methylene blue.
The invention also aims to provide the application of the methylene blue adsorbent in methylene blue adsorption, which can quickly and efficiently adsorb methylene blue and has good industrial application prospect.
According to the invention, a metal organic framework compound ZIF-67 is selected as an adsorbent main body, the ZIF-67 is loaded on a bacterial cellulose carrier, and the adsorbent can be recovered by filtering after adsorption is finished, so that the recovery operation of the adsorbent is simplified. The ZIF-67 is subjected to sulfonic group modification, and compared with the ZIF-67, the modified adsorbent is obviously improved in adsorption capacity, so that the methylene blue is quickly and efficiently adsorbed, and a new thought is provided for adsorption and separation of the methylene blue dye.
In order to achieve the purpose, the invention adopts the following technical scheme:
the methylene blue adsorbent comprises the active ingredient of sulfo-modified ZIF-67/bacterial cellulose, and is obtained by modifying the bacterial cellulose loaded with a metal organic framework compound ZIF-67 by using a sulfo group substance at least containing two sulfo groups. Wherein, one sulfonic group in the sulfonic group substance can react with Co (II) in ZIF-67, and the rest free sulfonic group can improve the adsorption effect on methylene blue. When sulfonic group is modified, the molar ratio of ZIF-67 to sulfonic substances is 1: 0.5-3. Preferably, the molar ratio of the ZIF-67 to the sulfonic acid group-containing substance is 1: 1 to 3, more preferably 1: 2 to 3.
Furthermore, the metal organic framework compound ZIF-67 of the present invention has been reported in the prior art, and those skilled in the art can synthesize ZIF-67 according to the methods reported in the prior art, for example, ZIF-67 can be synthesized by the methods reported in the literature [ R.Banerjee, science. 2008, 319 (5865): 939- > 943 ]. In one embodiment of the present invention, ZIF-67 is synthesized from cobalt nitrate hexahydrate and 2-methylimidazole in methanol at a 1:4 molar ratio.
Furthermore, in the invention, the adsorption effect is exerted mainly by sulfonic group modified ZIF-67, the bacterial cellulose is mainly used as a carrier, the carrier is solid and insoluble in solvents such as water, and the ZIF-67 is loaded on the carrier and can be uniformly dispersed, thus being convenient for collection and operation. The bacterial cellulose can be bacterial cellulose with any shape and molecular weight reported in the prior art, and is preferably bacterial cellulose with large size so as to facilitate the recycling of the adsorbent.
Furthermore, the mass ratio of the ZIF-67 to the bacterial cellulose is 1: 0.5-3. The loading capacity is too low, the ZIF-67 content in the adsorbent is low, and the adsorption effect is poor; the load is too large, and the ZIF-67 cannot be fully loaded on the bacterial cellulose. Preferably, the mass ratio of the ZIF-67 to the bacterial cellulose is 1: 0.8-3.
Experiments show that the adsorption effect of the ZIF-67/bacterial cellulose on methylene blue is poor, and the adsorption effect of the adsorbent on the methylene blue is greatly improved after the methylene blue is modified by adopting a sulfonic acid group. The sulfonic acid group-containing substance may be any substance having at least 2 sulfonic acid groups, for example, a sulfonic acid group dye having at least two sulfonic acid groups, and the like. The sulfonic dye can be aniline blue, acid fuchsin, acid chrome blue K, Congo red and other sulfonic dyes with at least 2 sulfonic groups, and aniline blue or acid fuchsin is preferred.
Furthermore, the sulfonic group modification is carried out by dispersing ZIF-67/bacterial cellulose into a sulfonic group substance water solution and stirring for reaction. The concentration of the sulfonic acid group substance aqueous solution is 50-600 mg/L, and the stirring reaction time is 10 min-3 h. The concentration of the sulfonic acid group substance aqueous solution and the stirring reaction time can be adjusted and matched according to actual needs, and the sulfonic acid group modification on the adsorbent can be realized in sufficient quantity.
The invention also provides a preparation method of the methylene blue adsorbent, which comprises the following steps:
(1) loading a metal organic framework compound ZIF-67 on bacterial cellulose to obtain ZIF-67/bacterial cellulose;
(2) and carrying out sulfonic group modification on the ZIF-67/bacterial cellulose to obtain the methylene blue adsorbent.
Further, in the step (1), dispersing the bacterial cellulose into methanol, adding cobalt nitrate hexahydrate, standing after complete dissolution, adding a methanol solution of 2-methylimidazole, performing hydrothermal reaction or standing reaction at normal temperature, filtering and washing after reaction to obtain the ZIF-67/bacterial cellulose.
Further, in the step (1) above, the molar ratio of cobalt nitrate hexahydrate and 2-methylimidazole may be any of the feasible molar ratios reported in the prior art, and these obtained ZIF-67 may be used in the present invention. In one embodiment of the invention, the molar ratio of cobalt nitrate hexahydrate to 2-methylimidazole is 1: 4.
Further, in the step (1), after the methanol solution of 2-methylimidazole is added, standing at normal temperature for reaction for 2-3 days, wherein the temperature of the hydrothermal reaction is 70-90 ℃ and the time of the hydrothermal reaction is 10-15 hours.
Further, in the step (2), dispersing the ZIF-67/bacterial cellulose into an aqueous solution of a sulfonic substance containing at least two sulfonic groups, stirring for sulfonic group modification, and then filtering to obtain the sulfonic group-modified ZIF-67/bacterial cellulose, namely the methylene blue adsorbent.
Further, in the step (2), the concentration of the sulfonic acid group substance aqueous solution containing at least two sulfonic acid groups is 50-600 mg/L, and the modification time is 10 min-3 h.
The invention also provides a method for adsorbing methylene blue by adopting the methylene blue adsorbent, which comprises the following steps: the methylene blue adsorbent is added into a water environment containing methylene blue to adsorb the methylene blue in the water environment.
Further, when adsorbing methylene blue, the methylene blue adsorbent is immersed in an aqueous solution containing methylene blue, stirred and adsorbed for a period of time, and then filtered, and the adsorbent is recovered. The invention is mainly realized by-SO modified in the adsorbent3 -With methylene blue-N+(CH3)2The adsorption of methylene blue is realized by the electrostatic effect, and the adsorption effect of the adsorbent on the methylene blue is obviously improved after the adsorbent is modified by sulfonic acid groups.
Furthermore, the method is suitable for an aqueous solution or waste liquid with methylene blue concentration of 50-1000 mg/L during methylene blue adsorption. The adsorbent is added into an aqueous solution or waste liquid containing methylene blue according to the molar ratio of ZIF-67 to methylene blue of 1: 0.2-6. The adsorption time is generally 10 min-3 h.
Furthermore, the adsorbent can realize efficient adsorption separation of methylene blue, is convenient to separate from a solution, and can be recycled. The adsorbent is immersed in a water environment containing methylene blue for sufficient adsorption, then the adsorbent is separated by filtration, and then the adsorbent is immersed in ethanol to resolve the methylene blue, so that the adsorbent can be recycled.
The adsorbent takes a sulfonic group modified metal organic framework compound ZIF-67 loaded bacterial cellulose as an effective component, and the-SO in the adsorbent is modified by sulfonic groups of ZIF-67 through a multi-sulfonic group substance3 -With methylene blue-N+(CH3)2The adsorbent has strong electrostatic effect, greatly improves the adsorption capacity of the adsorbent to methylene blue, and can realize the quick and efficient adsorption of the methylene blue. The adsorbent is easy to synthesize, the sulfonic group modification step is simple, the reaction condition is mild, the cost is low, the reaction yield is high, the methylene blue adsorption speed is high, the adsorption capacity is large, and the industrial production is easy to realize.
Drawings
FIG. 1 is an XRD pattern of a ZIF-67/bacterial cellulose composite.
Detailed Description
The present invention is described in detail below by way of examples, and it should be noted that the examples are only for further illustration of the present invention, but not for limiting the scope thereof.
In the following examples, bacterial cellulose, aniline blue (C) was used32H25N3Na2O9S3) Acid fuchsin (C)20H17N3Na2O9S3) Acid chrome blue K (C)16H9N2Na3O12S3) Congo red (C)32H22N6Na2O6S2) Are commercially available.
Example 1
Bacterial cellulose (40 mg) was dispersed in a methanol (25 mL) solvent, and cobalt nitrate hexahydrate (250 mg, 0.859 mmol) was added thereto, and left to stand for 2 days after it was completely dissolved. 2-methylimidazole (283 mg, 3.447 mmol) was dissolved in methanol (25 mL) solvent, and then poured into the above cobalt nitrate hexahydrate solution, stirred for 10min, and allowed to stand at room temperature for 2 days. And after the obtained product is subjected to suction filtration, leaching for 3 times by using methanol, and performing suction filtration to obtain the bacterial cellulose composite material loaded with the ZIF-67, namely ZIF-67/bacterial cellulose. The mass of the obtained ZIF-67/bacterial cellulose was 78.5mg, and the ZIF-67 loading amount, which is the mass content of ZIF-67 in ZIF-67/bacterial cellulose, was 49.0% by conversion.
The prepared sample is analyzed by powder XRD, the obtained result is shown in figure 1, and the XRD pattern of the obtained sample proves that the sample is the bacterial cellulose composite material loaded with ZIF-6.
Example 2
ZIF-67/bacterial cellulose was prepared as in example 1, except that: after the 2-methylimidazole solution was added, the loading reaction was carried out in the following manner: and (3) placing the mixed reactants into a 100mL reaction kettle, reacting for 10h at 80 ℃, carrying out suction filtration, leaching with methanol (60 mL), collecting a filter cake, and drying to obtain the ZIF-67/bacterial cellulose. The mass of ZIF-67/bacterial cellulose was 74.5mg, and the ZIF-67 loading was calculated to be 46.3%.
Example 3
Bacterial cellulose (40 mg) was dispersed in a methanol (10 mL) solvent, and cobalt nitrate hexahydrate (75 mg, 0.257 mmol) was added thereto, and left to stand for 2 days after it was completely dissolved. 2-methylimidazole (85 mg, 1.03 mmol) was dissolved in methanol (10 mL) solvent, and then poured into the above cobalt nitrate hexahydrate solution, stirred for 10min, and allowed to stand at room temperature for 2 days. And after the obtained product is subjected to suction filtration, leaching for 3 times by using methanol, and performing suction filtration to obtain the bacterial cellulose composite material loaded with the ZIF-67, namely ZIF-67/bacterial cellulose. The mass of ZIF-67/bacterial cellulose was 53.7mg, and the amount of ZIF-67 loaded was calculated to be 25.5%.
Example 4
Bacterial cellulose (40 mg) was dispersed in a methanol (10 mL) solvent, and cobalt nitrate hexahydrate (100 mg, 0.343 mmol) was added thereto, and left to stand for 2 days after it was completely dissolved. 2-methylimidazole (113 mg, 1.376 mmol) was dissolved in methanol (10 mL) solvent, and then poured into the above cobalt nitrate hexahydrate solution, stirred for 10min, and allowed to stand at room temperature for 2 days. And after the obtained product is subjected to suction filtration, leaching for 3 times by using methanol, and performing suction filtration to obtain the bacterial cellulose composite material loaded with the ZIF-67, namely ZIF-67/bacterial cellulose. The mass of ZIF-67/bacterial cellulose was 58.1mg, and the ZIF-67 loading was calculated to be 31.2%.
Example 5
ZIF-67/bacterial cellulose was prepared as in example 1, except that: bacterial cellulose (40 mg) was dispersed in a methanol (15 mL) solvent, and cobalt nitrate hexahydrate (150 mg, 0.515 mmol) was added thereto, and left to stand for 2 days after it was completely dissolved. 2-methylimidazole (170 mg, 2.070 mmol) was dissolved in methanol (15 mL) solvent, and then poured into the above cobalt nitrate hexahydrate solution, stirred for 10min, and allowed to stand at room temperature for 2 days. The other steps are unchanged. The mass of ZIF-67/bacterial cellulose was 67.2mg, and the amount of ZIF-67 loaded was calculated to be 40.5%.
Example 6
ZIF-67/bacterial cellulose was prepared as in example 1, except that: bacterial cellulose (40 mg) was dispersed in a methanol (30 mL) solvent, and cobalt nitrate hexahydrate (265 mg, 0.911 mmol) was added thereto, and left to stand for 2 days after it was completely dissolved. 2-methylimidazole (300 mg, 3.654 mmol) was dissolved in methanol (30 mL) solvent, and then poured into the above cobalt nitrate hexahydrate solution, stirred for 10min, and allowed to stand at room temperature for 2 days. The other steps are unchanged. The mass of ZIF-67/bacterial cellulose was 88.7mg, and the ZIF-67 loading was calculated to be 54.9%.
Example 7
The ZIF-67/bacterial cellulose prepared in example 1 was subjected to sulfonic acid group modification, and the procedure was as follows: ZIF-67/bacterial cellulose (8 mg) is dispersed in different sulfonic acid group dye water solutions (40mL, 600mg/L), stirred for 1-2h at normal temperature, filtered, collected and dried, and weighed to obtain the adsorbent.
The sulfonic acid group dye used, the stirring time, and the mass of the resulting adsorbent are shown in table 1 below.
Carrying out methylene blue adsorption on the 4 prepared adsorbents with modified sulfonic groups, and comprising the following steps: directly adding the adsorbent into a methylene blue aqueous solution (40mL, 600mg/L), stirring at normal temperature for 2h, performing suction filtration to collect a filter cake, drying, and weighing to obtain the mass of the adsorbent after adsorbing the methylene blue. And calculating the mass difference of the adsorbent before and after adsorption, namely the adsorption quantity of the adsorbent to methylene blue. The specific results are shown in table 2 below:
example 8
ZIF-67/bacterial cellulose (8 mg) prepared in examples 2, 3, 4, 5, and 6 were dispersed in an aqueous aniline blue solution (40mL, 600mg/L), and after stirring at room temperature for 1 hour, the resulting mixture was collected by suction filtration, and after drying, the resulting filter cake was weighed to obtain 20.8 mg, 13.8mg, 15.2mg, 18.9mg, and 21.2mg of adsorbents, respectively.
The 5 prepared adsorbents are subjected to methylene blue adsorption, and the steps are as follows: directly adding the adsorbent into a methylene blue aqueous solution (40mL, 600mg/L), stirring at normal temperature for 2h, performing suction filtration to collect a filter cake, drying, and weighing to obtain the mass of the adsorbent after adsorbing the methylene blue. And calculating the mass difference of the adsorbent before and after adsorption, namely the adsorption quantity of the adsorbent to methylene blue. The specific results are shown in table 3 below:
comparative example 1
The ZIF-67/bacterial cellulose prepared in example 1 was directly used as an adsorbent without sulfonic acid group modification, and the following steps were performed:
ZIF-67/bacterial cellulose (8 mg) from example 1 was directly added to an aqueous methylene blue solution (40mL, 600mg/L), stirred at room temperature for 2 hours, and then the cake was collected by suction filtration, dried and weighed to give a mass of 9.1 mg. Wherein the adsorption amount of methylene blue was 1.1 mg.
Comparative example 2
Cobalt nitrate hexahydrate (250 mg, 0.859 mmol) was added to methanol (25 mL) and allowed to stand for 2 days after complete dissolution. 2-methylimidazole (282.5 mg, 3.441 mmol) was dissolved in methanol (25 mL) solvent, and then poured into the above cobalt nitrate hexahydrate solution, stirred for 10min, and allowed to stand at room temperature for 2 days. And after the obtained product is subjected to suction filtration, leaching for 3 times by using methanol, and performing suction filtration to obtain ZIF-67.
ZIF-67 (8 mg) was directly added to an aqueous methylene blue solution (40mL, 600mg/L), stirred at room temperature for 2 hours, filtered to collect a cake, dried and weighed to a mass of 9.0 mg. Wherein the adsorption amount of methylene blue was 1.0 mg.
Comparative example 3
The ZIF-67/bacterial cellulose prepared in example 1 was subjected to sulfonic acid group modification, and the procedure was as follows: ZIF-67/bacterial cellulose (8 mg) is dispersed in methyl orange water solution (40mL, 600mg/L), stirred for 2h at normal temperature, filtered to collect filter cake, dried and weighed to obtain 10.5mg of product, and the obtained product is the adsorbent.
The adsorbent (10.5 mg) was directly added to an aqueous methylene blue solution (40mL, 600mg/L), stirred at room temperature for 2 hours, filtered to collect a cake, dried and weighed to give a mass of 11.4 mg. Wherein the adsorption amount of methylene blue was 0.9 mg.
The method for efficiently adsorbing methylene blue in an aqueous solution by using the ZIF-67/bacterial cellulose modified by the polysulfonic substance as the adsorbent is described in detail through the embodiment. The invention is not limited to the disclosure of this embodiment. It will be understood by those skilled in the art that the synthetic method of the present invention can be performed equivalently or modified without departing from the spirit of the present invention, and the preparation method thereof is not limited to the contents disclosed in the examples.
Claims (10)
1. A methylene blue adsorbent is characterized in that: carrying out sulfonic group modification on bacterial cellulose loaded with a metal organic framework compound ZIF-67 by using a sulfonic group substance at least containing two sulfonic groups, wherein the molar ratio of the ZIF-67 to the sulfonic group substance is 1:0.5 to 3.
2. The methylene blue adsorbent according to claim 1, wherein: when sulfonic group is modified, the molar ratio of ZIF-67 to sulfonic group substances is 1: 1 to 3.
3. The methylene blue adsorbent according to claim 1 or 2, characterized in that: the mass ratio of the ZIF-67 to the bacterial cellulose is 1: 0.5-3, preferably 1: 0.8-3.
4. The methylene blue adsorbent according to claim 1 or 2, characterized in that: the sulfonic substance is a sulfonic dye, preferably aniline blue, acid fuchsin, acid chrome blue K or Congo red, and more preferably aniline blue or acid fuchsin.
5. The methylene blue adsorbent according to claim 1 or 2, characterized in that: ZIF-67 was prepared from cobalt nitrate hexahydrate and 2-methylimidazole in methanol at a molar ratio of 1: 4.
6. A method for preparing the methylene blue adsorbent as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps:
(1) loading a metal organic framework compound ZIF-67 on bacterial cellulose to obtain ZIF-67/bacterial cellulose;
(2) and carrying out sulfonic group modification on the ZIF-67/bacterial cellulose to obtain the methylene blue adsorbent.
7. The method of claim 6, wherein: in the step (1), dispersing the bacterial cellulose into methanol, adding cobalt nitrate hexahydrate, standing after complete dissolution, adding a methanol solution of 2-methylimidazole, performing hydrothermal reaction or standing reaction at normal temperature after adding, filtering and washing after reaction to obtain ZIF-67/bacterial cellulose.
8. The method of claim 6, wherein: in the step (2), the ZIF-67/bacterial cellulose is dispersed into an aqueous solution of a sulfonic substance at least containing two sulfonic groups, and then the mixture is stirred for sulfonic group modification, and then the mixture is filtered to obtain the sulfonic group modified ZIF-67/bacterial cellulose, namely the methylene blue adsorbent.
9. The method of claim 8, wherein: the concentration of the sulfonic acid group substance aqueous solution containing at least two sulfonic acid groups is 50-600 mg/L, and the modification time is 10 min-3 h.
10. A methylene blue adsorption method is characterized in that: adsorbing methylene blue in an aqueous environment using the methylene blue adsorbent of any one of claims 1 to 5.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1094728A (en) * | 1996-06-18 | 1998-04-14 | Bio Polymer Res:Kk | Novel adsorbent |
| CN105502564A (en) * | 2016-01-08 | 2016-04-20 | 牛和林 | Adsorbing agent capable of selectively removing dyes containing sulfonic acid groups in wastewater and method of adsorbing agent |
| CN110170315A (en) * | 2019-04-15 | 2019-08-27 | 绍兴文理学院元培学院 | A kind of fiber base aeroge adsorbent and its application in absorption dyeing waste-water |
| CN110265669A (en) * | 2019-05-30 | 2019-09-20 | 南京源恒能源科技有限公司 | N doping carbonization bacteria cellulose-base graded porous carbon composite material and preparation method |
-
2020
- 2020-05-07 CN CN202010377436.8A patent/CN111569835A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1094728A (en) * | 1996-06-18 | 1998-04-14 | Bio Polymer Res:Kk | Novel adsorbent |
| CN105502564A (en) * | 2016-01-08 | 2016-04-20 | 牛和林 | Adsorbing agent capable of selectively removing dyes containing sulfonic acid groups in wastewater and method of adsorbing agent |
| CN110170315A (en) * | 2019-04-15 | 2019-08-27 | 绍兴文理学院元培学院 | A kind of fiber base aeroge adsorbent and its application in absorption dyeing waste-water |
| CN110265669A (en) * | 2019-05-30 | 2019-09-20 | 南京源恒能源科技有限公司 | N doping carbonization bacteria cellulose-base graded porous carbon composite material and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| LIU YANFENG ET AL.: "In situ modification of ZIF-67 with multi-sulfonated dyes for great enhanced methylene blue adsorption via synergistic effect", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| ZHEN JIANG ET AL.: "LDH nanocages synthesized with MOF templates and their high performance as supercapacitors", 《NANOSCALE》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113713776A (en) * | 2021-09-10 | 2021-11-30 | 天津工业大学 | Preparation method of ZIF-67-loaded wool fabric and application of wool fabric in printing and dyeing wastewater |
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