CN110327986B - Modified nano cellulose fiber, preparation method and application of modified nano cellulose fiber in catalyzing methylene blue degradation - Google Patents
Modified nano cellulose fiber, preparation method and application of modified nano cellulose fiber in catalyzing methylene blue degradation Download PDFInfo
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- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 179
- 239000000835 fiber Substances 0.000 title claims abstract description 179
- 229960000907 methylthioninium chloride Drugs 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 230000015556 catabolic process Effects 0.000 title abstract description 15
- 238000006731 degradation reaction Methods 0.000 title abstract description 15
- 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 1
- 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 claims abstract description 97
- 239000002244 precipitate Substances 0.000 claims abstract description 92
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229940043237 diethanolamine Drugs 0.000 claims abstract description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 132
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 76
- 238000000034 method Methods 0.000 claims description 73
- 230000000593 degrading effect Effects 0.000 claims description 50
- 238000005406 washing Methods 0.000 claims description 42
- 230000007935 neutral effect Effects 0.000 claims description 33
- 239000000706 filtrate Substances 0.000 claims description 29
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 24
- 238000004537 pulping Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 14
- 239000011449 brick Substances 0.000 claims description 13
- 238000000502 dialysis Methods 0.000 claims description 13
- 238000006073 displacement reaction Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 10
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010009 beating Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 244000166124 Eucalyptus globulus Species 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 238000010908 decantation Methods 0.000 description 55
- 239000008367 deionised water Substances 0.000 description 42
- 229910021641 deionized water Inorganic materials 0.000 description 42
- 239000000243 solution Substances 0.000 description 40
- 238000003756 stirring Methods 0.000 description 34
- 239000000203 mixture Substances 0.000 description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 27
- 239000003086 colorant Substances 0.000 description 24
- 241000219927 Eucalyptus Species 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 13
- 238000002791 soaking Methods 0.000 description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 11
- 238000005903 acid hydrolysis reaction Methods 0.000 description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 11
- 229910052603 melanterite Inorganic materials 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 11
- 238000004064 recycling Methods 0.000 description 11
- 238000007789 sealing Methods 0.000 description 11
- 239000000725 suspension Substances 0.000 description 11
- 208000005156 Dehydration Diseases 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 10
- 238000006297 dehydration reaction Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- -1 papermaking Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Catalysts (AREA)
Abstract
The disclosure provides a modified nano cellulose fiber, a preparation method and an application of the modified nano cellulose fiber in catalyzing methylene blue degradation, wherein the preparation method comprises the following steps: adding nano cellulose fiber to the solution containing H2O2And NH3·H2Carrying out oxidation treatment in the solution of O, adding the nano cellulose fiber after oxidation treatment into the solution containing ferric salt and ferrous salt for dipping, and then adding a precipitator containing hydroxide radical to form precipitate so as to load the nano cellulose fiber with Fe3O4Reacting the precipitate with a silane coupling agent to make the nano-cellulose fiber undergo hydrophobic modification, thereby obtaining the hydrophobic modified CNF @ Fe3O4Hydrophobically modified CNF @ Fe3O4And carrying out grafting reaction with diethanol amine to obtain the modified nano cellulose fiber. The modified nanocellulose fibers of the present disclosure have the ability to degrade methylene blue stain and can be recovered by magnetic attraction.
Description
Technical Field
The disclosure belongs to the field of preparation of bio-based materials, and relates to modified nano cellulose fibers, a preparation method and application of the modified nano cellulose fibers in catalysis of methylene blue degradation.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
Methylene blue, also known as methylene blue, and basic lake blue, is a phenothiazine salt type aromatic heterocyclic compound. Methylene blue is a cationic organic dye which is commonly used in industry and is widely applied to the fields of textile, leather, papermaking, dye, plastics and the like. At present, a large amount of waste water dye is generated in the fields of industrial papermaking, chemical industry, dyeing and weaving and the like, so that environmental pollution, reduction of photosynthesis capacity of aquatic plants, nausea, vomiting and cancer lesion of human beings are caused. As far as the inventor knows, the existing methylene blue treatment needs to adopt a large amount of chemicals, and the chemicals also bring environmental pollution.
Disclosure of Invention
In order to solve the defects of the prior art, the purpose of the present disclosure is to combine green renewable materials to treat methylene blue in wastewater, reduce the use of chemicals, and improve the treatment efficiency, thereby providing modified nanocellulose fibers, which can be used for sewage treatment, are environmentally friendly and can be recycled, and a preparation method and an application of catalyzing the degradation of methylene blue.
In order to achieve the purpose, the technical scheme of the disclosure is as follows:
in a first aspect, the present disclosure provides a modified nanocellulose fiber comprising nanocellulose fiber, said nanocellulose fiber being loaded with Fe3O4The nano cellulose fiber is grafted with amine, and the nano cellulose fiber is modified by a silane coupling agent.
The nano cellulose fiber is a renewable substance with the advantages of degradability, biocompatibility and the like, and has larger length-diameter ratio and high crystallinity and strength. The application of the nano cellulose fiber is limited due to the characteristics of easy flocculation, high hydrophilicity and the like of the nano cellulose fiber.
The present disclosure is carried out by grafting amino and loading Fe3O4The modified nano cellulose fiber is obtained, has the characteristic of catalyzing and degrading methylene blue, and has superparamagnetism, so that the modified nano cellulose fiber can be recycled for multiple times through magnetic recovery.
In a second aspect, the present disclosure provides a method for preparing modified nanocellulose fibers by adding nanocellulose fibers to a solution containing H2O2And NH3·H2Carrying out oxidation treatment in the solution of O, adding the nano cellulose fiber after oxidation treatment into the solution containing ferric salt and ferrous salt for dipping, and then adding a precipitator containing hydroxide radical to form precipitate so as to load the nano cellulose fiber with Fe3O4Reacting the precipitate with a silane coupling agent to obtain the nanocellulose fibersHydrophobic modification is carried out on the vitamin, so as to obtain hydrophobic modified CNF @ Fe3O4Hydrophobically modified CNF @ Fe3O4And carrying out grafting reaction with diethanol amine to obtain the modified nano cellulose fiber.
The preparation method disclosed by the invention does not need an organic solvent, and is green and environment-friendly.
In a third aspect, the disclosure provides an application of the modified nanocellulose fiber or the modified nanocellulose fiber obtained by the preparation method of the modified nanocellulose fiber in catalyzing methylene blue degradation.
The modified nanocellulose fiber provided by the disclosure can be used for efficiently catalyzing and degrading methylene blue in a short time, and the modified nanocellulose fiber can be recycled for multiple times.
In a fourth aspect, the active ingredient of the methylene blue degradation catalyst is the modified nano cellulose fiber or the modified nano cellulose fiber obtained by the preparation method of the modified nano cellulose fiber.
In a fifth aspect, a method for degrading methylene blue comprises adding a catalyst and NaBH to a solution containing methylene blue4Carrying out reaction; the catalyst is the modified nano cellulose fiber, the modified nano cellulose fiber obtained by the preparation method of the modified nano cellulose fiber or the methylene blue degradation catalyst.
The beneficial effect of this disclosure does:
(1) the method takes the nano cellulose fiber as a raw material, and the modification is carried out under the water system condition, so that the method has the advantages of environmental protection and reproducibility.
(2) The modified nano cellulose fiber disclosed by the invention has the capability of degrading a methylene blue coloring agent, can be recovered through magnetic attraction, and is a cleaning product.
(3) The preparation method disclosed by the invention is simple, strong in degradation capability, strong in practicability and easy to popularize.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In order to reduce the pollution of a chemical reagent for degrading methylene blue to the environment, the disclosure provides modified nano cellulose fibers, a preparation method and application of the modified nano cellulose fibers in catalyzing the degradation of the methylene blue.
In an exemplary embodiment of the present disclosure, a modified nanocellulose fiber is provided, including a nanocellulose fiber, the nanocellulose fiber supporting Fe3O4The nano cellulose fiber is grafted with amine, and the nano cellulose fiber is modified by a silane coupling agent.
The present disclosure is carried out by grafting amino and loading Fe3O4The modified nano cellulose fiber is obtained, has the characteristic of catalyzing and degrading methylene blue, and has superparamagnetism, so that the modified nano cellulose fiber can be recycled for multiple times through magnetic recovery.
In one or more embodiments of this embodiment, the nanocellulose fibers are combined with Fe3O4The mass ratio of (A) to (B) is 2: 2.5-3.5.
In one or more embodiments of this embodiment, the nanocellulose fibers are 200-2000 nm in length and 5-20 nm in diameter.
In a second embodiment of the present disclosure, a method for preparing modified nanocellulose fibers is provided, wherein nanocellulose fibers are added to a solution containing H2O2And NH3·H2Performing oxidation treatment in O solution to obtain oxidized nanocelluloseAdding fibers into a solution containing ferric salt and ferrous salt for impregnation, and adding a precipitator containing hydroxide radicals to form precipitates, so that the nano cellulose fibers are supported with Fe3O4Reacting the precipitate with a silane coupling agent to make the nano-cellulose fiber undergo hydrophobic modification, thereby obtaining the hydrophobic modified CNF @ Fe3O4Hydrophobically modified CNF @ Fe3O4And carrying out grafting reaction with diethanol amine to obtain the modified nano cellulose fiber.
In one or more embodiments of this embodiment, H2O2And NH3·H2The mass ratio of O is 0.8-1.2: 1.
In one or more embodiments of this embodiment, the oxidation treatment time is 0.5 to 1.5 hours.
In one or more embodiments of the embodiment, the oxidized nanocellulose fibers are added into a solution containing ferric salt and ferrous salt, the solution is stirred until the color of the solution becomes brick red, then the solution is heated, a precipitator is added to adjust the solution to be alkaline, and the solution is stirred until the color of the solution becomes black, so that the precipitate is obtained.
In the series of embodiments, the heating temperature is 50-60 ℃.
In this series of examples, the precipitant was ammonia.
In the series of examples, the pH of the solution is adjusted to 11.0-12.0.
In one or more embodiments of this embodiment, the temperature at which the precipitate reacts with the silane coupling agent is 65 to 75 ℃.
In one or more embodiments of this embodiment, the silane coupling agent is 3-aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, or gamma- (2, 3-glycidoxy) propyltrimethoxysilane.
In one or more embodiments of this embodiment, after the precipitate is reacted with the silane coupling agent, the reaction product is washed with water and ethanol until the filtrate is free of chloride ions.
In one or more embodiments of the present disclosure, the mass ratio of the nanocellulose fibers to the silane coupling agent is 10: 0.9-1.1.
In one or more embodiments of this embodiment, the temperature of the grafting reaction is 45 to 55 ℃.
In one or more embodiments of this embodiment, the diethanolamine is present in an amount of 1 to 30 wt.% of the mass of the nanocellulose fibers. Experiments show that when the dosage of the diethanolamine is less than 5 wt.%, the catalytic degradation effect of the modified nano cellulose fiber on the methylene blue coloring agent is poor; when the dosage of the diethanolamine is more than 20 wt%, the influence of the dosage of the diethanolamine on the catalytic degradation effect of the methylene blue is not great. Therefore, the effect is better when the dosage of the diethanolamine is 5 wt.% to 20 wt.%.
In one or more embodiments of the embodiment, a method for preparing nano cellulose fibers is further provided, the method comprises the steps of soaking and defibering eucalyptus pulp, dewatering after pulping to obtain pulp, hydrolyzing the pulp under acid regulation, and then performing ultrasonic cell pulverization treatment to obtain the nano cellulose fibers.
In the series of embodiments, the slurry is beaten to a beating degree of 45-50 DEG SR.
In this series of examples, the acid used for hydrolysis was not less than 60wt.% sulfuric acid. The mass ratio of the sulfuric acid to the slurry is 17.5-18.5: 1.
In the series of embodiments, the hydrolysis temperature is 45-55 ℃.
In this series of examples, hydrolysis was followed by washing to a supernatant pH of no higher than 3, and then the pellet was subjected to displacement dialysis until the dialysate was neutral.
In a third embodiment of the present disclosure, an application of the modified nanocellulose fiber or the modified nanocellulose fiber obtained by the preparation method of the modified nanocellulose fiber in catalysis of methylene blue degradation is provided.
The modified nanocellulose fiber provided by the disclosure can be used for efficiently catalyzing and degrading methylene blue in a short time, and the modified nanocellulose fiber can be recycled for multiple times.
In a fourth embodiment of the present disclosure, a methylene blue degradation catalyst is provided, and the active ingredient is the modified nanocellulose fiber or the modified nanocellulose fiber obtained by the preparation method of the modified nanocellulose fiber.
In a fifth embodiment of the disclosure, a method for degrading methylene blue is provided, wherein a catalyst and NaBH are added into a solution containing methylene blue4Carrying out reaction; the catalyst is the modified nano cellulose fiber, the modified nano cellulose fiber obtained by the preparation method of the modified nano cellulose fiber or the methylene blue degradation catalyst.
In one or more examples of this embodiment, the concentration of methylene blue in the solution of methylene blue is from 0.5mmol/L to 5 mmol/L.
In one or more embodiments of the present disclosure, the solid-to-liquid ratio of the modified nanocellulose fiber to the methylene blue solution is 100-400: 50, mg: and (mL).
In order to make the technical solutions of the present disclosure more clearly understood by those skilled in the art, the technical solutions of the present disclosure will be described in detail below with reference to specific embodiments.
Example 1
A preparation method of modified nano cellulose fibers with a function of catalyzing and degrading methylene blue coloring agents comprises the following specific steps:
1) preparing modified nano cellulose fiber: a) soaking the eucalyptus pulp board in deionized water until the eucalyptus pulp board is completely fluffed, pulping until the pulping degree is 48 DEG SR, dehydrating, sealing and balancing for 12h, and measuring the moisture for later use. b) Taking a proper amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a mass ratio of acid pulp of 18: 1 adding a proper amount of 64% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) The precipitate was taken out, treated in an ultrasonic cell disruptor at 1200W for 30min, filtered and the water content was measured. d) 10g of the suspension of the oven-dried nano cellulose fibers is placed in a three-neck flask, and 100mLH is added2O2(30% by mass, the same applies hereinafter) and NH3·H2Mixing O (37 wt%, the same below) at a mass ratio of 1: 1, mechanically stirring at room temperature for 1h, and separating with deionized waterThe heart was washed to neutrality, the precipitate was collected and the moisture was measured. e) Taking 8g of the treated nano cellulose fiber in a three-neck flask, and adding FeCl3·6H2O and FeSO4·7H2O is added in a molar ratio of 2:1 was dispersed in 100mL of deionized water and transferred to a three-necked flask and stirred at room temperature for 30min until the solution appeared brick red. Heating in water bath to 55 ℃, and adding 2mol/L NH3·H2And O, adjusting the pH value to 11.0-12.0, stirring for 2h until the solution system is black, washing to be neutral by a magnetic decantation method, collecting precipitates and measuring the water content. The obtained precipitate is CNF @ Fe3O4. f) Taking 8g of absolute dry CNF @ Fe3O4Adding 160mL of water ethanol (the mass ratio of water to ethanol is 1: 3), adding 0.8g of 3-aminopropyltriethoxysilane, stirring in a water bath at 70 ℃ for 6 hours, washing by using a water ethanol magnetic decantation method until filtrate does not contain chloride ions, collecting precipitate, measuring moisture, and obtaining precipitate, namely CNF @ Fe3O4-APTS. g) Taking the 6g absolute dry CNF @ Fe3O4-APTS in three-neck flask, adding 0.3g diethanolamine, continuously introducing nitrogen, reacting for 12h in 50 ℃ water bath, washing by using aqueous ethanol magnetic decantation method until the filtrate does not contain chloride ion, collecting precipitate, and drying in 60 ℃ oven for standby.
2) The modified nano cellulose fiber is used for catalyzing and degrading a methylene blue coloring agent: a) putting 50mL of methylene blue with the concentration of 1mmol/L into a beaker, adding 100mg of modified nano cellulose fiber and 300mg of NaBH at the same time4Mechanically stirring for 5min, recovering the modified nano cellulose fiber by a magnetic decantation method, collecting the upper layer liquid, scanning under an ultraviolet-visible spectrophotometer, and calculating the concentration of the upper layer liquid. And recovering the modified nano cellulose fiber by a magnetic decantation method and recycling.
Example 2
A preparation method of modified nano cellulose fibers with a function of catalyzing and degrading methylene blue coloring agents comprises the following specific steps:
1) preparing modified nano cellulose fiber: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking a proper amount of slurry (compared withOven-dried pulp) is placed in a three-neck flask, and the mass ratio of the acid pulp is 18: 1 adding a proper amount of 64% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) The precipitate was taken out, treated in an ultrasonic cell disruptor at 1200W for 30min, filtered and the water content was measured. d) 10g of the suspension of the oven-dried nano cellulose fibers is placed in a three-neck flask, and 100mLH is added2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, then centrifugally washing the mixture to be neutral by using deionized water, collecting precipitates and measuring the moisture. e) Taking 8g of the treated nano cellulose fiber in a three-neck flask, and adding FeCl3·6H2O and FeSO4·7H2O is added in a molar ratio of 2:1 was dispersed in 100mL of deionized water and transferred to a three-necked flask and stirred at room temperature for 30min until the solution appeared brick red. Heating in water bath to 55 ℃, and adding 2mol/L NH3·H2And O, adjusting the pH value to 11.0-12.0, stirring for 2h until the solution system is black, washing to be neutral by a magnetic decantation method, collecting precipitates and measuring the water content. The obtained precipitate is CNF @ Fe3O4. f) Taking 8g of absolute dry CNF @ Fe3O4160mL of aqueous ethanol (water to ethanol mass ratio of 1: 3) was added, 0.8g of gamma-methacryloxypropyltrimethoxysilane was added, the mixture was stirred in a 70 ℃ water bath for 6 hours, washed by aqueous ethanol magnetic decantation until the filtrate contained no chloride ions, and the precipitate was collected and the water content was measured. The obtained precipitate is CNF @ Fe3O4-MPS. g) Taking the 6g absolute dry CNF @ Fe3O4Adding 0.6g of diethanolamine into the three-neck flask, continuously introducing nitrogen, reacting in a water bath at 50 ℃ for 12 hours, washing by using a water-ethanol magnetic decantation method until the filtrate does not contain chloride ions, collecting the precipitate, and drying in an oven at 60 ℃ for later use.
2) The modified nano cellulose fiber is used for catalyzing and degrading a methylene blue coloring agent: a) putting 50mL of methylene blue with the concentration of 1mmol/L into a beaker, adding 100mg of modified nano cellulose fiber and 300mg of NaBH at the same time4Mechanically stirring for 5min, recovering modified nanometer cellulose fiber by magnetic decantation, and collecting the upper liquidAnd collecting and scanning under an ultraviolet-visible spectrophotometer to calculate the concentration of the compound. And recovering the modified nano cellulose fiber by a magnetic decantation method and recycling.
Example 3
A preparation method of modified nano cellulose fibers with a function of catalyzing and degrading methylene blue coloring agents comprises the following specific steps:
1) preparing modified nano cellulose fiber: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking a proper amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a mass ratio of acid pulp of 18: 1 adding a proper amount of 64% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) The precipitate was taken out, treated in an ultrasonic cell disruptor at 1200W for 30min, filtered and the water content was measured. d) 10g of the suspension of the oven-dried nano cellulose fibers is placed in a three-neck flask, and 100mLH is added2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, centrifugally washing the mixture by using deionized water until the mixture is neutral, collecting precipitate and measuring the moisture. e) Taking 8g of the treated nano cellulose fiber in a three-neck flask, and adding FeCl3·6H2O and FeSO4·7H2O is added in a molar ratio of 2:1 was dispersed in 100mL of deionized water and transferred to a three-necked flask and stirred at room temperature for 30min until the solution appeared brick red. Heating in water bath to 55 ℃, and adding 2mol/L NH3·H2And O, adjusting the pH value to 11.0-12.0, stirring for 2h until the solution system is black, washing to be neutral by a magnetic decantation method, collecting precipitates and measuring the water content. The obtained precipitate is CNF @ Fe3O4. f) Taking 8g of absolute dry CNF @ Fe3O4160mL of aqueous ethanol (water to ethanol mass ratio of 1: 3) was added, 0.8g of gamma-methacryloxypropyltrimethoxysilane was added, the mixture was stirred in a 70 ℃ water bath for 6 hours, washed by aqueous ethanol magnetic decantation until the filtrate contained no chloride ions, and the precipitate was collected and the water content was measured. The obtained precipitate is CNF @ Fe3O4-MPS. g) Taking the 6g absolute dry CNF @ Fe3O4Adding 0.9g of diethanolamine into the three-neck flask, continuously introducing nitrogen, reacting in a water bath at 50 ℃ for 12 hours, washing by using a water-ethanol magnetic decantation method until the filtrate does not contain chloride ions, collecting the precipitate, and drying in an oven at 60 ℃ for later use.
2) The modified nano cellulose fiber is used for catalyzing and degrading a methylene blue coloring agent: a) putting 50mL of methylene blue with the concentration of 1mmol/L into a beaker, adding 100mg of modified nano cellulose fiber and 300mg of NaBH at the same time4Mechanically stirring for 5min, recovering the modified nano cellulose fiber by a magnetic decantation method, collecting the upper layer liquid, scanning under an ultraviolet-visible spectrophotometer, and calculating the concentration of the upper layer liquid. And recovering the modified nano cellulose fiber by a magnetic decantation method and recycling.
Example 4
A preparation method of modified nano cellulose fibers with a function of catalyzing and degrading methylene blue coloring agents comprises the following specific steps:
1) preparing modified nano cellulose fiber: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking a proper amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a mass ratio of acid pulp of 18: 1 adding a proper amount of 64% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) The precipitate was taken out, treated in an ultrasonic cell disruptor at 1200W for 30min, filtered and the water content was measured. d) 10g of the suspension of the oven-dried nano cellulose fibers is placed in a three-neck flask, and 100mLH is added2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, then centrifugally washing the mixture to be neutral by using deionized water, collecting precipitates and measuring the moisture. e) Taking 8g of the treated nano cellulose fiber in a three-neck flask, and adding FeCl3·6H2O and FeSO4·7H2O is added in a molar ratio of 2:1 was dispersed in 100mL of deionized water and transferred to a three-necked flask, and stirred at room temperature for 30min to dissolveThe liquid is brick red. Heating in water bath to 55 ℃, and adding 2mol/L NH3·H2And O, adjusting the pH value to 11.0-12.0, stirring for 2h until the solution system is black, washing to be neutral by a magnetic decantation method, collecting precipitates and measuring the water content. The obtained precipitate is CNF @ Fe3O4. f) Taking 8g of absolute dry CNF @ Fe3O4160mL of aqueous ethanol (water to ethanol mass ratio of 1: 3) was added, 0.8g of gamma- (2, 3-epoxypropane) propyltrimethoxysilane was added, the mixture was stirred in a water bath at 70 ℃ for 6 hours, and the filtrate was washed by magnetic decantation with aqueous ethanol until it contained no chloride ions, and the precipitate was collected and the water content was measured. The obtained precipitate is CNF @ Fe3O4EPPM. g) Taking the 6g absolute dry CNF @ Fe3O4EPPM is put into a three-neck flask, 1.2g of diethanolamine is added, nitrogen is continuously introduced, the reaction is carried out in a water bath at 50 ℃ for 12 hours, the filtrate is washed by the water-ethanol magnetic decantation method until the filtrate does not contain chloride ions, and the precipitate is collected and dried in an oven at 60 ℃ for standby.
2) The modified nano cellulose fiber is used for catalyzing and degrading a methylene blue coloring agent: a) putting 50mL of methylene blue with the concentration of 1mmol/L into a beaker, adding 100mg of modified nano cellulose fiber and 300mg of NaBH at the same time4Mechanically stirring for 5min, recovering the modified nano cellulose fiber by a magnetic decantation method, collecting the upper layer liquid, scanning under an ultraviolet-visible spectrophotometer, and calculating the concentration of the upper layer liquid. And recovering the modified nano cellulose fiber by a magnetic decantation method and recycling.
Example 5
A preparation method of modified nano cellulose fibers with a function of catalyzing and degrading methylene blue coloring agents comprises the following specific steps:
1) preparing modified nano cellulose fiber: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking a proper amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a mass ratio of acid pulp of 18: 1 adding a proper amount of 64% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) Taking out the precipitate, and subjecting to ultrasoundThe cells were treated in a sonicator at 1200W for 30min, filtered and the water content measured. d) 10g of the suspension of the oven-dried nano cellulose fibers is placed in a three-neck flask, and 100mLH is added2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, then centrifugally washing the mixture to be neutral by using deionized water, collecting precipitates and measuring the moisture. e) Taking 8g of the treated nano cellulose fiber in a three-neck flask, and adding FeCl3·6H2O and FeSO4·7H2O is added in a molar ratio of 2:1 was dispersed in 100mL of deionized water and transferred to a three-necked flask and stirred at room temperature for 30min until the solution appeared brick red. Heating in water bath to 55 ℃, and adding 2mol/L NH3·H2And O, adjusting the pH value to 11.0-12.0, stirring for 2h until the solution system is black, washing to be neutral by a magnetic decantation method, collecting precipitates and measuring the water content. The obtained precipitate is CNF @ Fe3O4. f) Taking 8g of absolute dry CNF @ Fe3O4160mL of aqueous ethanol (water to ethanol mass ratio of 1: 3) was added, 0.8g of 3-aminopropyltriethoxysilane was added, the mixture was stirred in a 70 ℃ water bath for 6 hours, washed by aqueous ethanol magnetic decantation until the filtrate contained no chloride ion, and the precipitate was collected and the water content was measured. The obtained precipitate is CNF @ Fe3O4-APTS. g) Taking the 6g absolute dry CNF @ Fe3O4-APTS in three-neck flask, adding 1.2g diethanolamine, continuously introducing nitrogen, reacting for 12h in 50 ℃ water bath, washing by using aqueous ethanol magnetic decantation method until the filtrate does not contain chloride ion, collecting precipitate, and drying in 60 ℃ oven for standby.
2) The modified nano cellulose fiber is used for catalyzing and degrading a methylene blue coloring agent: a) putting 50mL of methylene blue with the concentration of 1mmol/L into a beaker, adding 200mg of modified nano cellulose fiber and simultaneously adding 300mg of NaBH4Mechanically stirring for 5min, recovering the modified nano cellulose fiber by a magnetic decantation method, collecting the upper layer liquid, scanning under an ultraviolet-visible spectrophotometer, and calculating the concentration of the upper layer liquid. And recovering the modified nano cellulose fiber by a magnetic decantation method and recycling.
Example 6
A preparation method of modified nano cellulose fibers with a function of catalyzing and degrading methylene blue coloring agents comprises the following specific steps:
1) preparing modified nano cellulose fiber: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking a proper amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a mass ratio of acid pulp of 18: 1 adding a proper amount of 64% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) The precipitate was taken out, treated in an ultrasonic cell disruptor at 1200W for 30min, filtered and the water content was measured. d) 10g of the suspension of the oven-dried nano cellulose fibers is placed in a three-neck flask, and 100mLH is added2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, then centrifugally washing the mixture to be neutral by using deionized water, collecting precipitates and measuring the moisture. e) Taking 8g of the treated nano cellulose fiber in a three-neck flask, and adding FeCl3·6H2O and FeSO4·7H2O is added in a molar ratio of 2:1 was dispersed in 100mL of deionized water and transferred to a three-necked flask and stirred at room temperature for 30min until the solution appeared brick red. Heating in water bath to 55 ℃, and adding 2mol/L NH3·H2And O, adjusting the pH value to 11.0-12.0, stirring for 2h until the solution system is black, washing to be neutral by a magnetic decantation method, collecting precipitates and measuring the water content. The obtained precipitate is CNF @ Fe3O4. f) Taking 8g of absolute dry CNF @ Fe3O4160mL of aqueous ethanol (water to ethanol mass ratio of 1: 3) was added, 0.8g of gamma-methacryloxypropyltrimethoxysilane was added, the mixture was stirred in a 70 ℃ water bath for 6 hours, washed by aqueous ethanol magnetic decantation until the filtrate contained no chloride ions, and the precipitate was collected and the water content was measured. The obtained precipitate is CNF @ Fe3O4-MPS. g) Taking the 6g absolute dry CNF @ Fe3O4MPS is put into a three-neck flask, 1.2g of diethanolamine is added, nitrogen is continuously introduced, the reaction is carried out in a water bath at 50 ℃ for 12 hours, the mixture is washed by the water-ethanol magnetic decantation method until the filtrate does not contain chloride ions, the precipitate is collected and dried in an oven at 60 ℃ for standby.
2) The modified nano cellulose fiber is used for catalyzing and degrading a methylene blue coloring agent: a) putting 50mL of methylene blue with the concentration of 1mmol/L into a beaker, adding 300mg of modified nano cellulose fiber and 300mg of NaBH simultaneously4Mechanically stirring for 5min, recovering the modified nano cellulose fiber by a magnetic decantation method, collecting the upper layer liquid, scanning under an ultraviolet-visible spectrophotometer, and calculating the concentration of the upper layer liquid. And recovering the modified nano cellulose fiber by a magnetic decantation method and recycling.
Example 7
A preparation method of modified nano cellulose fibers with a function of catalyzing and degrading methylene blue coloring agents comprises the following specific steps:
1) preparing modified nano cellulose fiber: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking a proper amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a mass ratio of acid pulp of 18: 1 adding a proper amount of 64% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) The precipitate was taken out, treated in an ultrasonic cell disruptor at 1200W for 30min, filtered and the water content was measured. d) 10g of the suspension of the oven-dried nano cellulose fibers is placed in a three-neck flask, and 100mLH is added2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, then centrifugally washing the mixture to be neutral by using deionized water, collecting precipitates and measuring the moisture. e) Taking 8g of the treated nano cellulose fiber in a three-neck flask, and adding FeCl3·6H2O and FeSO4·7H2O is added in a molar ratio of 2:1 was dispersed in 100mL of deionized water and transferred to a three-necked flask and stirred at room temperature for 30min until the solution appeared brick red. Heating in water bath to 55 ℃, and adding 2mol/L NH3·H2And O, adjusting the pH value to 11.0-12.0, stirring for 2h until the solution system is black, washing to be neutral by a magnetic decantation method, collecting precipitates and measuring the water content. The obtained precipitate is CNF @ Fe3O4. f) Taking 8g of absolute dry CNF @ Fe3O4160mL of aqueous ethanol (water to ethanol mass ratio of 1: 3) was added, 0.8g of 3-aminopropyltriethoxysilane was added, the mixture was stirred in a 70 ℃ water bath for 6 hours, washed by aqueous ethanol magnetic decantation until the filtrate contained no chloride ion, and the precipitate was collected and the water content was measured. The obtained precipitate is CNF @ Fe3O4-APTS. g) Taking the 6g absolute dry CNF @ Fe3O4-APTS in three-necked flask, adding 1.2g diethanolamine, continuously introducing nitrogen, reacting in 50 ℃ water bath for 12h, washing with aqueous ethanol magnetic decantation until the filtrate does not contain chloride ion, collecting precipitate, and drying in 60 ℃ oven for standby.
2) The modified nano cellulose fiber is used for catalyzing and degrading a methylene blue coloring agent: a) putting 50mL of methylene blue with the concentration of 1mmol/L into a beaker, adding 400mg of modified nano cellulose fiber and 300mg of NaBH at the same time4Mechanically stirring for 5min, recovering the modified nano cellulose fiber by a magnetic decantation method, collecting the upper layer liquid, scanning under an ultraviolet-visible spectrophotometer, and calculating the concentration of the upper layer liquid. And recovering the modified nano cellulose fiber by a magnetic decantation method and recycling.
Example 8
A preparation method of modified nano cellulose fibers with a function of catalyzing and degrading methylene blue coloring agents comprises the following specific steps:
1) preparing modified nano cellulose fiber: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking a proper amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a mass ratio of acid pulp of 18: 1 adding a proper amount of 64% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) The precipitate was taken out, treated in an ultrasonic cell disruptor at 1200W for 30min, filtered and the water content was measured. d) 10g of the suspension of the oven-dried nano cellulose fibers is placed in a three-neck flask, and 100mLH is added2O2And NH3·H2Mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, and then centrifugally washing the mixture by using deionized waterTo neutrality, the precipitate was collected and the moisture was measured. e) Taking 8g of the treated nano cellulose fiber in a three-neck flask, and adding FeCl3·6H2O and FeSO4·7H2O is added in a molar ratio of 2:1 was dispersed in 100mL of deionized water and transferred to a three-necked flask and stirred at room temperature for 30min until the solution appeared brick red. Heating in water bath to 55 ℃, and adding 2mol/L NH3·H2And O, adjusting the pH value to 11.0-12.0, stirring for 2h until the solution system is black, washing to be neutral by a magnetic decantation method, collecting precipitates and measuring the water content. The obtained precipitate is CNF @ Fe3O4. f) Taking 8g of absolute dry CNF @ Fe3O4160mL of aqueous ethanol (water to ethanol mass ratio of 1: 3) was added, 0.8g of gamma-methacryloxypropyltrimethoxysilane was added, the mixture was stirred in a 70 ℃ water bath for 6 hours, washed by aqueous ethanol magnetic decantation until the filtrate contained no chloride ions, and the precipitate was collected and the water content was measured. The obtained precipitate is CNF @ Fe3O4-MPS. g) Taking the 6g absolute dry CNF @ Fe3O4MPS is put into a three-neck flask, 1.2g of diethanolamine is added, nitrogen is continuously introduced, the reaction is carried out in a water bath at 50 ℃ for 12 hours, the mixture is washed by the water-ethanol magnetic decantation method until the filtrate does not contain chloride ions, the precipitate is collected and dried in an oven at 60 ℃ for standby.
2) The modified nano cellulose fiber is used for catalyzing and degrading a methylene blue coloring agent: a) putting 50mL of methylene blue with the concentration of 1.5mmol/L into a beaker, adding 200mg of modified nano cellulose fiber and 300mg of NaBH at the same time4Mechanically stirring for 5min, recovering the modified nano cellulose fiber by a magnetic decantation method, collecting the upper layer liquid, scanning under an ultraviolet-visible spectrophotometer, and calculating the concentration of the upper layer liquid. And recovering the modified nano cellulose fiber by a magnetic decantation method and recycling.
Example 9
A preparation method of modified nano cellulose fibers with a function of catalyzing and degrading methylene blue coloring agents comprises the following specific steps:
1) preparing modified nano cellulose fiber: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking a proper amount of slurryPlacing the mixture (compared with oven-dried pulp) in a three-neck flask, and mixing the mixture in a syrup mass ratio of 18: 1 adding a proper amount of 64% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) The precipitate was taken out, treated in an ultrasonic cell disruptor at 1200W for 30min, filtered and the water content was measured. d) 10g of the suspension of the oven-dried nano cellulose fibers is placed in a three-neck flask, and 100mLH is added2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, then centrifugally washing the mixture to be neutral by using deionized water, collecting precipitates and measuring the moisture. e) Taking 8g of the treated nano cellulose fiber in a three-neck flask, and adding FeCl3·6H2O and FeSO4·7H2O is added in a molar ratio of 2:1 was dispersed in 100mL of deionized water and transferred to a three-necked flask and stirred at room temperature for 30min until the solution appeared brick red. Heating in water bath to 55 ℃, and adding 2mol/L NH3·H2And O, adjusting the pH value to 11.0-12.0, stirring for 2h until the solution system is black, washing to be neutral by a magnetic decantation method, collecting precipitates and measuring the water content. The obtained precipitate is CNF @ Fe3O4. f) Taking 8g of absolute dry CNF @ Fe3O4160mL of aqueous ethanol (water to ethanol mass ratio of 1: 3) was added, 0.8g of 3-aminopropyltriethoxysilane was added, the mixture was stirred in a 70 ℃ water bath for 6 hours, washed by aqueous ethanol magnetic decantation until the filtrate contained no chloride ion, and the precipitate was collected and the water content was measured. The obtained precipitate is CNF @ Fe3O4-APTS. g) Taking the 6g absolute dry CNF @ Fe3O4-APTS in three-necked flask, adding 1.2g diethanolamine, continuously introducing nitrogen, reacting in 50 ℃ water bath for 12h, washing with aqueous ethanol magnetic decantation until the filtrate does not contain chloride ion, collecting precipitate, and drying in 60 ℃ oven for standby.
2) The modified nano cellulose fiber is used for catalyzing and degrading a methylene blue coloring agent: a) putting 50mL of 2mmol/L methylene blue into a beaker, adding 200mg of modified nano cellulose fiber and simultaneously adding 300mg of NaBH4Mechanically stirring for 5min, recovering modified nanometer cellulose fiber by magnetic decantation, collecting the upper layer liquid and collectingScanning the mixture with an ultraviolet-visible spectrophotometer to calculate the concentration of the mixture. And recovering the modified nano cellulose fiber by a magnetic decantation method and recycling.
Example 10
A preparation method of modified nano cellulose fibers with a function of catalyzing and degrading methylene blue coloring agents comprises the following specific steps:
1) preparing modified nano cellulose fiber: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking a proper amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a mass ratio of acid pulp of 18: 1 adding a proper amount of 64% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) The precipitate was taken out, treated in an ultrasonic cell disruptor at 1200W for 30min, filtered and the water content was measured. d) 10g of the suspension of the oven-dried nano cellulose fibers is placed in a three-neck flask, and 100mLH is added2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, then centrifugally washing the mixture to be neutral by using deionized water, collecting precipitates and measuring the moisture. e) Taking 8g of the treated nano cellulose fiber in a three-neck flask, and adding FeCl3·6H2O and FeSO4·7H2O is added in a molar ratio of 2:1 was dispersed in 100mL of deionized water and transferred to a three-necked flask and stirred at room temperature for 30min until the solution appeared brick red. Heating in water bath to 55 ℃, and adding 2mol/L NH3·H2And O, adjusting the pH value to 11.0-12.0, stirring for 2h until the solution system is black, washing to be neutral by a magnetic decantation method, collecting precipitates and measuring the water content. The obtained precipitate is CNF @ Fe3O4. f) Taking 8g of absolute dry CNF @ Fe3O4160mL of aqueous ethanol (water to ethanol mass ratio of 1: 3) was added, 0.8g of gamma-methacryloxypropyltrimethoxysilane was added, the mixture was stirred in a 70 ℃ water bath for 6 hours, washed by aqueous ethanol magnetic decantation until the filtrate contained no chloride ions, and the precipitate was collected and the water content was measured. The obtained precipitate is CNF @ Fe3O4-MPS. g) Taking the 6g absolute dry CNF @ Fe3O4MPS is put into a three-neck flask, 1.2g of diethanolamine is added, nitrogen is continuously introduced, the reaction is carried out in a water bath at 50 ℃ for 12 hours, the mixture is washed by the water-ethanol magnetic decantation method until the filtrate does not contain chloride ions, the precipitate is collected and dried in an oven at 60 ℃ for standby.
2) The modified nano cellulose fiber is used for catalyzing and degrading a methylene blue coloring agent: a) putting 50mL of 2.5mmol/L methylene blue into a beaker, adding 200mg of modified nano cellulose fiber and 300mg of NaBH at the same time4Mechanically stirring for 5min, recovering the modified nano cellulose fiber by a magnetic decantation method, collecting the upper layer liquid, scanning under an ultraviolet-visible spectrophotometer, and calculating the concentration of the upper layer liquid. And recovering the modified nano cellulose fiber by a magnetic decantation method and recycling.
Example 11
A preparation method of modified nano cellulose fibers with a function of catalyzing and degrading methylene blue coloring agents comprises the following specific steps:
1) preparing modified nano cellulose fiber: a) placing the eucalyptus pulp board in deionized water for soaking until the eucalyptus pulp board is completely defibered, pulping until the pulping degree is 48 DEG SR, performing dehydration treatment, sealing and balancing for 12h, and then measuring the moisture for later use. b) Taking a proper amount of pulp (compared with oven-dried pulp) and placing the pulp in a three-neck flask in a mass ratio of acid pulp of 18: 1 adding a proper amount of 64% concentrated sulfuric acid, carrying out acid hydrolysis reaction in a water bath at 50 ℃ for 1h, adding deionized water to stop the reaction after the reaction is finished, carrying out centrifugal washing until the pH of a supernatant is 3, and carrying out precipitation displacement dialysis until a dialysate is neutral. c) The precipitate was taken out, treated in an ultrasonic cell disruptor at 1200W for 30min, filtered and the water content was measured. d) 10g of the suspension of the oven-dried nano cellulose fibers is placed in a three-neck flask, and 100mLH is added2O2And NH3·H2And mechanically stirring the O mixed solution (the mass ratio is 1: 1) at room temperature for 1h, then centrifugally washing the mixture to be neutral by deionized water, collecting precipitates and measuring the moisture. e) Taking 8g of the treated nano cellulose fiber in a three-neck flask, and adding FeCl3·6H2O and FeSO4·7H2O is added in a molar ratio of 2:1 was dispersed in 100mL of deionized water and transferred to a three-necked flask, and stirred at room temperature for 30min to a solutionIs brick red. Heating in water bath to 55 ℃, and adding 2mol/L NH3·H2And O, adjusting the pH value to 11.0-12.0, stirring for 2h until the solution system is black, washing to be neutral by a magnetic decantation method, collecting precipitates and measuring the water content. The obtained precipitate is CNF @ Fe3O4. f) Taking 8g of absolute dry CNF @ Fe3O4160mL of aqueous ethanol (water to ethanol mass ratio of 1: 3) was added, 0.8g of gamma- (2, 3-glycidoxy) propyltrimethoxysilane was added, the mixture was stirred in a water bath at 70 ℃ for 6 hours, washed by aqueous ethanol magnetic decantation until the filtrate contained no chloride ions, and the precipitate was collected and the water content was measured. The obtained precipitate is CNF @ Fe3O4EPPM. g) Taking the 6g absolute dry CNF @ Fe3O4EPPM in three-necked flask, adding 1.2g of diethanolamine, and continuously introducing nitrogen, reaction in 50 ℃ water bath for 12h, washing with aqueous ethanol magnetic decantation until the filtrate contains no chloride ion, collecting the precipitate, and drying in 60 ℃ oven for standby.
2) The modified nano cellulose fiber is used for catalyzing and degrading a methylene blue coloring agent: a) putting 50mL of 3mmol/L methylene blue into a beaker, adding 200mg of modified nano cellulose fiber and simultaneously adding 300mg of NaBH4Mechanically stirring for 5min, recovering the modified nano cellulose fiber by a magnetic decantation method, collecting the upper layer liquid, scanning under an ultraviolet-visible spectrophotometer, and calculating the concentration of the upper layer liquid. And recovering the modified nano cellulose fiber by a magnetic decantation method and recycling.
And (3) performance testing:
the concentration of methylene blue remaining in the filtrate after methylene blue treatment with the modified nanocellulose fibers prepared in examples 1 to 11 was determined using the concentration of methylene blue in the filtrate as an index for performance testing. The test method comprises the following steps: respectively preparing methylene blue standard samples of 0.005g/L, 0.001g/L, 0.0015g/L, 0.002g/L and 0.0025g/L, placing the methylene blue standard samples in an ultraviolet-visible spectrophotometer to measure absorbance, and determining a standard curve as shown in Table 1. The filtrates were separately placed in an ultraviolet-visible spectrophotometer to measure absorbance, and the concentrations thereof were calculated from the standard curves, with the test results shown in table 2.
TABLE 1 methylene blue Standard sample UV-VIS Absorbance
| Methylene blue concentration/g/L | 0.0005 | 0.001 | 0.0015 | 0.002 | 0.0025 |
| absorbance/T% | 0.02286 | 0.03559 | 0.04033 | 0.04875 | 0.05715 |
According to calculation, the standard curve is that y is 16.827x +0.0151
Wherein x is the concentration of methylene blue, g/L; and y is the absorbance of ultraviolet and visible light, T%.
Table 2 removal rate of methylene blue from filtrate of methylene blue treated with modified nanocellulose fibers prepared in examples 1 to 11
It can be seen from table 2 that, after the nanocellulose fiber is modified by the method of the present invention, methylene blue can be efficiently catalytically degraded in a short time, and the modified nanocellulose fiber can be recycled for many times.
The above description is only a preferred embodiment of the present disclosure and is not intended to limit the present disclosure, and various modifications and changes may be made to the present disclosure by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present disclosure should be included in the protection scope of the present disclosure.
Claims (22)
1. A method for degrading methylene blue is characterized in that a catalyst and NaBH are added into a solution containing the methylene blue4Carrying out reaction; the catalyst is modified nano cellulose fiber, and the preparation method comprises the following steps:
adding nano cellulose fiber to the solution containing H2O2And NH3·H2Carrying out oxidation treatment in the solution of O, adding the nano cellulose fiber after oxidation treatment into the solution containing ferric salt and ferrous salt for dipping, and then adding a precipitator containing hydroxide radical to form precipitate so as to load the nano cellulose fiber with Fe3O4Reacting the precipitate with a silane coupling agent to make the nano-cellulose fiber undergo hydrophobic modification, thereby obtaining the hydrophobic modified CNF @ Fe3O4Hydrophobically modified CNF @ Fe3O4Carrying out grafting reaction with diethanol amine to obtain modified nano cellulose fibers;
the length of the nano cellulose fiber is 200-2000 nm, and the diameter is 5-20 nm;
the silane coupling agent is 3-aminopropyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane or gamma- (2, 3-glycidoxy) propyltrimethoxysilane.
2. The method of claim 1, wherein the method comprises mixing the nanocellulose fiber with Fe3O4The mass ratio of (A) to (B) is 2: 2.5-3.5.
3. The method for degrading methylene blue according to claim 1, wherein H is2O2And NH3·H2The mass ratio of O is 0.8-1.2: 1.
4. The method for degrading methylene blue according to claim 1, wherein the oxidation treatment time is 0.5 to 1.5 hours.
5. The method for degrading methylene blue according to claim 1, wherein the oxidized nanocellulose fibers are added to a solution containing ferric salt and ferrous salt, the solution is stirred until the color of the solution becomes brick red, then the solution is heated, a precipitant is added to adjust the solution to be alkaline, and the solution is stirred until the color of the solution becomes black, so that a precipitate is obtained.
6. The method for degrading methylene blue according to claim 5, wherein the heating temperature is 50 to 60 ℃.
7. The method according to claim 1, wherein the precipitant is ammonia water.
8. The method for degrading methylene blue according to claim 5, wherein the pH of the solution is adjusted to 11.0 to 12.0.
9. The method for degrading methylene blue according to claim 1, wherein the temperature of the reaction of the precipitate with the silane coupling agent is 65 to 75 ℃.
10. The method for degrading methylene blue according to claim 1, wherein after the reaction of the precipitate with the silane coupling agent, the reaction product is washed with water and ethanol until the filtrate is free from chloride ions.
11. The method for degrading methylene blue, according to claim 1, wherein the mass ratio of the nanocellulose fibers to the silane coupling agent is 10:0.9 to 1.1.
12. The method for degrading methylene blue according to claim 1, wherein the temperature of the grafting reaction is 45 to 55 ℃.
13. The method for degrading methylene blue according to claim 1, wherein the amount of diethanolamine is 1 to 30 wt.% based on the mass of the nanocellulose fibers.
14. The method for degrading methylene blue according to claim 13, wherein the amount of diethanolamine used is 5 to 20 wt.%.
15. The method for degrading methylene blue according to claim 1, wherein the method for preparing the nano cellulose fiber comprises the steps of immersing and defibering eucalyptus pulp, pulping, dewatering to obtain a pulp, hydrolyzing the pulp under acid regulation, and performing ultrasonic cell pulverization to obtain the nano cellulose fiber.
16. The method for degrading methylene blue according to claim 15, wherein the slurry is beaten to a degree of beating of 45 to 50 ° SR.
17. The method for degrading methylene blue according to claim 16, wherein the acid used for hydrolysis is not less than 60wt.% sulfuric acid.
18. The method for degrading methylene blue according to claim 17, wherein a volume ratio of sulfuric acid to the slurry is 17.5 to 18.5: 1.
19. The method for degrading methylene blue according to claim 15, wherein the hydrolysis temperature is 45 to 55 ℃.
20. The method for degrading methylene blue according to claim 15, wherein the hydrolysis is followed by washing until the pH of the supernatant is not higher than 3, and then the precipitate is subjected to displacement dialysis until the dialysate is neutral.
21. The method for degrading methylene blue according to claim 1, wherein the concentration of methylene blue in the solution of methylene blue is 0.5 to 5 mmol/L.
22. The method for degrading methylene blue of claim 21, wherein the solid-to-liquid ratio of the modified nanocellulose fibers to the methylene blue solution is 100-400 mg: 50 mL.
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