CN117866277A - Super-hydrophilic/underwater super-oleophobic cellulose-based porous material and preparation method thereof - Google Patents
Super-hydrophilic/underwater super-oleophobic cellulose-based porous material and preparation method thereof Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 82
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- 238000002360 preparation method Methods 0.000 title abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000007710 freezing Methods 0.000 claims description 23
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- 238000000034 method Methods 0.000 claims description 17
- 238000005516 engineering process Methods 0.000 claims description 13
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- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 6
- -1 amino compound Chemical class 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 claims description 2
- QBJWYMFTMJFGOL-UHFFFAOYSA-N 2-hexadecyloxirane Chemical compound CCCCCCCCCCCCCCCCC1CO1 QBJWYMFTMJFGOL-UHFFFAOYSA-N 0.000 claims description 2
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- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 claims description 2
- 229960002442 glucosamine Drugs 0.000 claims description 2
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
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- NPGIHFRTRXVWOY-UHFFFAOYSA-N Oil red O Chemical compound Cc1ccc(C)c(c1)N=Nc1cc(C)c(cc1C)N=Nc1c(O)ccc2ccccc12 NPGIHFRTRXVWOY-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
-
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/02—Polyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2391/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a super-hydrophilic/underwater super-oleophobic cellulose-based porous material and a preparation method thereof, and relates to the field of material preparation. Due to the large number of hydroxyl groups (-OH), carboxyl groups (-COOH) on cellulose macromolecules, and the large number of amine groups (-NH) on amino compounds 2 ) Can capture water, form a stable hydration layer, prevent oil from contacting with the surface, endow the material with super-hydrophilic/underwater super-oleophobic wettability, and realize the oil adhesion resistance of the material. And because of the introduction of amino compounds, the porous material can adsorb heavy metal ions and organic dyes in water, has important practical application value, and achieves the aim of deeply purifying the water environment.
Description
Technical Field
The invention relates to a super-hydrophilic/underwater super-oleophobic cellulose-based porous material and a preparation method thereof, belonging to the field of material preparation.
Background
Petroleum leakage and the large volumes of oily sewage produced by various industries (e.g., textile, printing, paper, plastics, paint, and food) create increasingly serious water pollution, and pose a potential threat to the marine ecosystem and human health. Therefore, oil-water separation becomes more and more important and urgent. In order to solve the problems, the traditional oil absorption, oil skimming, precipitation and other technologies are used for separating the immiscible oil-water mixture, but the technologies not only generate serious secondary pollution, but also have poor separation effect on the oil-water emulsion stabilized by the surfactant. So far, a great deal of effort has been put into the research on emulsified oil separation materials, but most of the materials developed are mainly two-dimensional materials, and the materials can only be separated in the form of a filter membrane, and once the materials are polluted by emulsified oil, the wetting state of the materials is changed from a Cassie mode to a Wenzel mode, so that pores are blocked, the wetting selectivity is slow, the separation efficiency is reduced, and the flux is reduced. Therefore, it is necessary to design a porous material for preparing oil-adhesion resistance to achieve separation of oil-water emulsion with high stability.
However, oily wastewater from various industrial operations has a diverse and complex character, and studies have demonstrated that dyes, heavy metals, are also major contaminants that pose serious water safety problems. Organic dyes reduce photosynthesis in aquatic environments, causing water toxicity, mutagenicity, and carcinogenesis, threatening human health, and marine life. Also, the presence of heavy metals in water constitutes a serious health risk for humans and other organisms due to their non-biodegradability, high toxicity and bioaccumulation. Therefore, there is an urgent need to develop a multifunctional material having excellent oil-adhesion resistance, which can simultaneously remove insoluble emulsified oil, soluble organic dye and heavy metal ions.
Here, a simple strategy for separating high-stability oil-in-water emulsion and adsorbing heavy metal ions and organic dyes in water is provided for the purification and macroscopic treatment requirements of complex-component oil-containing water. And combining cellulose and amino compounds to obtain the super-moist porous material with various cross-linked network structures. A large number of hydroxyl groups (-OH), carboxyl groups (-COOH) and amino groups on cellulose macromoleculesThe compound has a plurality of amino groups (-NH) 2 ) Can capture water, form a stable hydration layer, prevent oil from contacting with the surface, endow the material with super-hydrophilic/underwater super-oleophobic wettability, and realize the oil adhesion resistance of the material. In addition, as a cationic polyelectrolyte, the amino compound and the negatively charged organic dye realize the adsorption of the organic dye in the water body through electrostatic attraction, hydrogen bonding and physical adsorption. In addition, primary amine groups on amino compounds can provide a large number of metal ion chelating coordination sites, and the adsorption of metal ions is realized by combining a high specific surface area. The cellulose-based crosslinking system can realize adjustable size and high porosity through directional freezing, and can separate oil-water emulsion and adsorb heavy metal ions and organic dye under the action of gravity, thereby achieving the purpose of deep purification of water environment.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a multifunctional super-hydrophilic/underwater super-oleophobic cellulose-based porous material according to the problem that the existing water treatment porous material has single performance. By adjusting the percentage of water in the cellulose-based crosslinking system, the adding proportion of amino compounds and crosslinking agents and other factors, the microstructure, wettability, oil-in-water emulsion separation performance and adsorption performance of heavy metal ions and organic dyes in the water body of the target product are controlled, and a new experimental technical route is provided for the super-wetting porous material for realizing water body purification in complex environments.
The technical scheme of the invention is realized as follows:
the preparation method of the super-hydrophilic/underwater super-oleophobic cellulose-based porous material comprises the steps of crosslinking cellulose, amino compounds and a crosslinking agent under alkaline conditions, and preparing the porous material by a freeze drying method, wherein the preparation method specifically comprises the following steps:
(1) Dispersing 10-100 parts by weight of cellulose in 5000-50000 parts by weight of deionized water to obtain a solution A containing cellulose;
(2) Adding 100-1000 parts by weight of an amino compound and 100-1000 parts by weight of a cross-linking agent into 5010-50100 parts by weight of a solution A, and adjusting the pH of the solution to 8-10 by sodium hydroxide to obtain a mixed solution B;
(3) Freezing the mixed solution B obtained in the step (2) for 3-6 hours by a low-temperature directional freezing technology, and then freeze-drying 48 and h to obtain the super-hydrophilic/underwater super-oleophobic cellulose-based porous material.
Compared with the prior art, the invention has the advantages that:
1. the invention uses water as a dispersion medium, does not use toxic and harmful solvents, and accords with the sustainable development trend of green environmental protection.
2. The porous material prepared by the method has a great amount of hydrophilic groups, so that the material is endowed with excellent oil-resistant adhesion and super-hydrophilic/underwater super-oleophobic performance; meanwhile, amino compounds endow the material with rich heavy metal ion chelating sites, can adsorb a large amount of heavy metal ions, and in addition, electrostatic attraction, hydrogen bonding and physical adsorption are generated between the amino compounds and the organic dye. Therefore, the super-wetting porous material prepared by the invention can separate oil-in-water emulsion with stable surfactant and adsorb heavy metal ions and organic dye in water body under the action of gravity, and has important practical application value.
3. The directional freezing technology is used for realizing the regulation and control of the pore parameters of the material, and the high-efficiency separation of the oil-in-water emulsion with high stability is realized based on the size screening effect.
Drawings
Fig. 1, surface wettability in air and underwater static oil contact angle diagrams of the product obtained in example 1, wherein fig. 1 (a) is a surface wettability in air of the product obtained in example 1, and fig. 1 (b) is an underwater static oil contact angle diagram of the product obtained in example 1;
FIG. 2 is a graph showing the macroscopic difference between the super-hydrophilic/underwater super-oleophobic cellulose-based porous materials prepared in example 1 and the porous materials prepared in comparative examples 1 and 2 in air and water;
FIG. 3, scanning electron microscope images of the superhydrophilic/underwater superoleophobic cellulose-based porous materials prepared in example 1 and the porous materials prepared in comparative examples 1 and 2, wherein FIG. 3 (a), FIG. 3 (a 1 ) Scanning electron microscopy images of the porous materials prepared in comparative example 1 at different magnifications, FIGS. 3 (b), 3 (b 1 ) Porous material prepared for comparative example 2Scanning electron microscope images at different magnifications, FIGS. 3 (c), 3 (c 1 ) Scanning electron microscopy images at different magnifications for the porous material prepared in example 1;
FIG. 4 is a graph of the underwater oil-resistant adhesion performance of the superhydrophilic/underwater superoleophobic cellulose-based porous material prepared in example 1;
FIG. 5, the super-hydrophilic/underwater super-oleophobic cellulose-based porous material prepared in example 1, is used for realizing a high-stability oil-in-water emulsion separation diagram under the action of gravity, wherein FIG. 5 (a) is a schematic diagram of a separation device, FIG. 5 (b) is a process diagram of oil-water emulsion separation, and FIG. 5 (c) and FIG. 5 (d) are macroscopic comparison diagrams before and after separation and corresponding fluorescent digital microscope diagrams using eyepiece-free inversion respectively;
FIG. 6, the super-hydrophilic/underwater super-oleophobic cellulose-based porous material prepared in example 1 realizes heavy metal ion adsorption drawing under the action of gravity, wherein FIG. 6 (a) is a process diagram for heavy metal ion adsorption, and FIG. 6 (b) is a macroscopic comparison diagram of solutions before and after adsorption;
FIG. 7, the organic dye adsorption drawing of the super-hydrophilic/underwater super-oleophobic cellulose-based porous material prepared in example 1 is realized by gravity, wherein FIG. 7 (a) is a process diagram of adsorbing soluble organic dye, and FIG. 7 (b) is a macroscopic comparison diagram of solutions before and after adsorption;
fig. 8, the super-hydrophilic/underwater super-oleophobic cellulose-based porous material prepared in example 1, is subjected to gravity action, and meanwhile, high-stability oil-in-water emulsion separation and organic dye and heavy metal ion adsorption drawing are realized, wherein fig. 8 (a) is a separation process diagram, fig. 8 (b) and fig. 8 (c) are respectively a macroscopic comparison diagram before and after separation and a corresponding eyepiece-free inverted fluorescent digital microscope diagram.
Detailed Description
The invention is described in further detail below in connection with the embodiments in the drawings, but is not to be construed as limiting the invention in any way.
Example 1: the super-hydrophilic/underwater super-oleophobic cellulose-based porous material is prepared by the following steps: dispersing 65 parts by weight of filamentous cellulose filaments in 12000 parts by weight of deionized water to obtain a solution A containing the filamentous cellulose filaments; 1000 parts by weight of polyethyleneimine and 500 parts by weight of epichlorohydrin are added to 12065 parts by weight of the solution A, and the pH of the solution is adjusted to 10 by sodium hydroxide, to obtain a mixed solution B; freezing 3 h of the mixed solution B obtained in the step (2) by a low-temperature directional freezing technology at the temperature of minus 30 ℃, and then freeze-drying 48 h to obtain the super-hydrophilic/underwater super-oleophobic cellulose-based porous material.
Example 2: the super-hydrophilic/underwater super-oleophobic cellulose-based porous material is prepared by the following steps: dispersing 20 parts by weight of filamentous cellulose filaments in 20000 parts by weight of deionized water to obtain a solution A containing the filamentous cellulose filaments; adding 500 parts by weight of polyether ammonia and 500 parts by weight of ethylene glycol diglycidyl ether to 20020 parts by weight of solution a, and adjusting the pH of the solution to 10 by sodium hydroxide to obtain a mixed solution B; freezing 3 h of the mixed solution B obtained in the step (2) by a low-temperature directional freezing technology at the temperature of minus 60 ℃, and then freeze-drying 48 h to obtain the super-hydrophilic/underwater super-oleophobic cellulose-based porous material.
Example 3: the super-hydrophilic/underwater super-oleophobic cellulose-based porous material is prepared by the following steps: dispersing 50 parts by weight of filamentous cellulose filaments in 18000 parts by weight of deionized water to obtain a solution A containing the filamentous cellulose filaments; 1200 parts by weight of isopropanolamine and 600 parts by weight of methylenebisacrylamide were added to 18050 parts by weight of solution a, and the pH of the solution was adjusted to 10 by sodium hydroxide to obtain a mixed solution B; freezing 3 h of the mixed solution B obtained in the step (2) by a low-temperature directional freezing technology at the temperature of minus 30 ℃, and then freeze-drying 48 h to obtain the super-hydrophilic/underwater super-oleophobic cellulose-based porous material.
Example 4: the super-hydrophilic/underwater super-oleophobic cellulose-based porous material is prepared by the following steps: dispersing 40 parts by weight of filamentous cellulose filaments in 16000 parts by weight of deionized water to obtain a solution A containing the filamentous cellulose filaments; 1100 parts by weight of butylamine and 700 parts by weight of epoxidized soybean oil were added to 16040 parts by weight of solution a, and the pH of the solution was adjusted to 10 by sodium hydroxide to obtain a mixed solution B; freezing 3 h of the mixed solution B obtained in the step (2) by a low-temperature directional freezing technology at the temperature of minus 30 ℃, and then freeze-drying 48 h to obtain the super-hydrophilic/underwater super-oleophobic cellulose-based porous material.
Example 5: the super-hydrophilic/underwater super-oleophobic cellulose-based porous material is prepared by the following steps: dispersing 58 parts by weight of filamentous cellulose filaments in 13000 parts by weight of deionized water to obtain a solution A containing the filamentous cellulose filaments; 1050 parts by weight of glucosamine and 640 parts by weight of 1, 2-epoxyoctadecane were added to 13058 parts by weight of solution A, and the pH of the solution was adjusted to 10 by sodium hydroxide to obtain a mixed solution B; freezing 3 h of the mixed solution B obtained in the step (2) by a low-temperature directional freezing technology at the temperature of minus 30 ℃, and then freeze-drying 48 h to obtain the super-hydrophilic/underwater super-oleophobic cellulose-based porous material.
Comparative example 1: a cellulose-based porous material comprising only cellulose, prepared by the steps of: dispersing 65 parts by weight of filamentous cellulose filaments in 12000 parts by weight of deionized water to obtain a solution A containing the filamentous cellulose filaments; adjusting the pH value of the solution to 10 by sodium hydroxide to obtain a mixed solution B; freezing 3 h of the mixed solution B obtained in the step (2) by a low-temperature directional freezing technology at the temperature of minus 30 ℃, and then freeze-drying 48 h to obtain the cellulose-based porous material without amino compounds and cross-linking agents.
Comparative example 2: a cellulose-based porous material free of amino compounds is prepared by the steps of: dispersing 65 parts by weight of filamentous cellulose filaments in 12000 parts by weight of deionized water to obtain a solution A containing the filamentous cellulose filaments; adding 500 parts by weight of epichlorohydrin to 12065 parts by weight of the solution A, and adjusting the pH of the solution to 10 by sodium hydroxide to obtain a mixed solution B; freezing 3 h of the mixed solution B obtained in the step (2) by a low-temperature directional freezing technology at the temperature of minus 30 ℃, and then freeze-drying 48 h to obtain the super-hydrophilic/underwater super-oleophobic cellulose-based porous material.
The preferred embodiments of the present invention will be described with reference to the accompanying drawings, which are to be understood as illustrative and not restrictive of the invention.
The performance test related in the embodiment of the invention is carried out according to the following method:
FIG. 1 is a graph showing the surface wettability in air and the contact angle of static oil under water of the product obtained in example 1. Wherein FIG. 1 (a) is a graph of the surface wettability in air of the product obtained in example 1, and FIG. 1 (b) is a graph of the contact angle of static oil under water of the product obtained in example 1. As shown in fig. 1 (a), water was dyed using a water-soluble pigment (bromophenol blue) at this time; the macroscopic wettability of chloroform by using oil-soluble pigment (oil red O) proves that the product obtained in example 1 is amphiphilic in air. Regarding the contact angle test, the superhydrophilic/underwater superoleophobic cellulose-based porous material prepared in example 1 was tested for surface water contact angle in air (WCA), oil Contact Angle (OCA) and Underwater Oil Contact Angle (UOCA) using an OCA25 type tester of Dataphysics company, germany. Among them, the product of example 1 was found to have an underwater oleophobic angle of 154.7 ° as seen in fig. 1 (b). In conclusion, the super-hydrophilic/underwater super-oleophobic characteristic is achieved.
FIG. 2 is a graph showing the macroscopic differences between the super-hydrophilic/underwater super-oleophobic cellulose-based porous materials prepared in example 1 and the porous materials prepared in comparative examples 1 and 2 in air and under water. The porous materials prepared in example 1 and comparative examples 1 and 2 were immersed in water for 24 h to observe swelling in water. From this, it can be seen that example 1 maintains its original shape in water, and that both comparative examples 1 and 2 have swelled, demonstrating that example 1 has better underwater mechanical properties.
FIG. 3 is a scanning electron microscope image of the superhydrophilic/underwater superoleophobic cellulose-based porous material prepared in example 1 and the porous materials prepared in comparative examples 1 and 2. The morphology of the porous materials prepared in example 1, comparative example 1 and comparative example 2 is analyzed by adopting a JSM-7500F scanning electron microscope, the accelerating voltage is 20.0 KV, and before the sample is tested, surface metal spraying treatment is needed. Wherein, fig. 3 (a), fig. 3 (a 1 ) Scanning electron microscopy images of the porous materials prepared in comparative example 1 at different magnifications, FIGS. 3 (b), 3 (b 1 ) Scanning electron microscopy images of the porous materials prepared in comparative example 2 at different magnifications, FIGS. 3 (c), 3 (c 1 ) Scanning electron microscopy images at different magnifications for the porous material prepared in example 1. Can be used forIn order to observe that the porous materials prepared in example 1 and comparative examples 1 and 2 all had uniform pore diameters, and from FIGS. 3 (c) and 3 (c) 1 ) It is seen that example 1 presents a vertical, micron-sized pore size, facilitating the separation of micro-nano oil-water emulsions.
FIG. 4 is a graph of the underwater oil-resistant adhesion performance of the superhydrophilic/underwater superoleophobic cellulose-based porous material prepared in example 1. The porous material prepared in example 1 was subjected to dyeing treatment with oil-soluble pigment (oil red O) in air, and then placed under water to observe the underwater oil-adhesion resistance. As can be seen from the figure, the porous material after dyeing in air starts to gather on the surface of the material at the moment when the porous material is placed under water, and floats upwards after five minutes, and the petroleum ether gathers on the water surface after ten minutes, at this time, the porous material returns to the original color, and the excellent underwater oil adhesion resistance is proved.
Fig. 5 is a graph showing the separation of the oil-in-water emulsion of the porous material of example 1 by gravity. Fig. 5 (a) is a schematic diagram of a separation device, fig. 5 (b) is a process diagram of oil-water emulsion separation, and fig. 5 (c) and fig. 5 (d) are macroscopic comparison diagrams before and after separation and corresponding fluorescent digital microscope diagrams using eyepiece-free inversion respectively. The super-hydrophilic/underwater super-oleophobic cellulose-based porous material prepared in example 1 was subjected to oil-water emulsion separation, and the specific test method comprises: (1) preparation of high-stability oil-water emulsion: at V Water and its preparation method ：V Oil (oil) =99: 1, 0.01 g/L SDS surfactant is added, and 1500 r/min is stirred for 3 h, thus obtaining the stable oil-in-water emulsion. (2) high-stability oil-water emulsion separation: as shown in FIG. 5 (a), the front end of the syringe with the needle removed is connected with a super-wetting material, and the water outlet end of the super-wetting material is connected with a conical flask (water collecting device). The prepared super-hydrophilic/underwater super-oleophobic cellulose-based porous material is used for collecting oil-water emulsion under the action of gravity, and the whole process is shown in fig. 5 (b). Finally, observing the liquid before and after separation by using an eyepiece-free inverted fluorescent digital microscope, and as can be seen from fig. 5 (c) and fig. 5 (d), the oil-in-water emulsion with milky color before separation has a plurality of oil drops; but is separated to obtainA clear aqueous phase was used and the filtrate after separation had no oil droplets observed.
FIG. 6 is a drawing showing the effect of heavy metal ion absorption by gravity of the porous material of example 1. Fig. 6 (a) is a process diagram of heavy metal ion adsorption, and fig. 6 (b) is a macroscopic comparison diagram of the solution before and after adsorption. The super-hydrophilic/underwater super-oleophobic cellulose-based porous material prepared in example 1 was subjected to a heavy metal ion adsorption performance test, and the specific test method comprises: (1) preparation of heavy metal ion/water mixture: at m Water and its preparation method ：m Heavy metal ions =10000: under the condition of 1, 1000 r/min is stirred for 1 h, so that heavy metal ions are uniformly dispersed. (2) heavy metal ion/water mixture separation: the front end of the syringe with the needle removed is connected with a super-wetting material, and the water outlet end of the super-wetting material is connected with a conical flask (water collecting device). The prepared super-hydrophilic/underwater super-oleophobic cellulose-based porous material realizes the adsorption of heavy metal ions under the action of gravity, and the whole process is shown in fig. 6 (a). As can be seen in FIG. 6 (b), the solution was blue before gravity separation, and a clear aqueous phase was obtained after separation.
FIG. 7 is a graph of the super-hydrophilic/underwater super-oleophobic cellulose-based porous material prepared in example 1 by gravity. Wherein, fig. 7 (a) is a process diagram of adsorbing the soluble organic dye, and fig. 7 (b) is a macroscopic comparison diagram of the solution before and after adsorption. The super-hydrophilic/underwater super-oleophobic cellulose-based porous material prepared in example 1 was subjected to an adsorption performance test of a soluble organic dye, and the specific test method comprises: (1) preparation of an organic dye/water mixture: at m Water and its preparation method ：m Organic dyes =10000: under the condition of 1, 1000 r/min is stirred for 1 h, so that the organic dye is uniformly dispersed. (2) separation of organic dye/water mixture: the front end of the syringe with the needle removed is connected with a super-wetting material, and the water outlet end of the super-wetting material is connected with a conical flask (water collecting device). The prepared super-hydrophilic/underwater super-oleophobic cellulose-based porous material realizes the adsorption of organic dye under the action of gravity, and the whole process is shown in fig. 7 (a). As can be seen in FIG. 7 (b), the solution before gravity separation was yellow, and a clear aqueous phase was obtained after separation.
FIG. 8 is a drawing showing the realization of the separation of oil-in-water emulsion with high stability and the absorption of organic dye and heavy metal ions by gravity of the super-hydrophilic/underwater super-oleophobic cellulose-based porous material prepared in example 1. Fig. 8 (a) is a separation process diagram, and fig. 8 (b) and fig. 8 (c) are macroscopic comparison diagrams before and after separation and corresponding inverted fluorescence digital microscope diagrams using no eyepiece. The superhydrophilic/underwater superoleophobic cellulose-based porous material prepared in example 1 was subjected to simultaneous separation of high-stability oil-in-water emulsion and adsorption performance test of organic dye and heavy metal ions. The specific test method comprises the following steps: (1) Preparation of high stability oil-in-water emulsion/organic dye/heavy metal ion/water mixture: at m Water and its preparation method ：m Heavy metal ions ：m Organic dyes =10000: 1:1 with the oil-in-water emulsion prepared as described above according to V Organic dye/heavy metal ion mixed solution ：V Oil-in-water emulsion =1: 1, mixing, and stirring for 2 h at 2000 r/min to uniformly disperse heavy metal ions, organic dye and high-stability oil-in-water emulsion. (2) High stability oil-in-water emulsion/organic dye/heavy metal ion/water mixture: the front end of the syringe with the needle removed is connected with a super-wetting material, and the water outlet end of the super-wetting material is connected with a conical flask (water collecting device). The prepared super-hydrophilic/underwater super-oleophobic cellulose-based porous material realizes the separation of the oil-in-water emulsion with high stability and the adsorption of organic dye and heavy metal ions through the action of gravity, and the whole process is shown in fig. 8 (a). The liquids before and after separation were observed using an eyepiece-free inverted fluorescent digital microscope, and as demonstrated by fig. 8 (b) and 8 (c), there were a number of oil droplets in the emulsion of high stability oil-in-water/organic dye/heavy metal ion/water mixture of milky yellow before separation, a transparent aqueous phase was obtained after separation, and no oil droplets were observed in the filtrate after separation.
The present invention is not limited to the above-mentioned embodiments, but is not limited to the above-mentioned embodiments, and any person skilled in the art can make some changes or modifications to the above-mentioned embodiments without departing from the scope of the present invention.
Claims (6)
1. A super-hydrophilic/underwater super-oleophobic cellulose-based porous material is characterized in that the porous material is prepared by carrying out a crosslinking reaction on cellulose, amino compounds and a crosslinking agent under an alkaline condition to realize the crosslinking of the cellulose and the amino compounds, the self-crosslinking of the cellulose and the amino compounds, obtaining a system with various network structures through the electrostatic interaction between the cellulose and the amino compounds and the intermolecular and intramolecular hydrogen bonding, carrying out directional freezing on the system to obtain a vertical pore structure, and finally, preparing the porous material through freeze drying.
2. The superhydrophilic/underwater superoleophobic cellulose-based porous material according to claim 1, characterized in that the porous material is prepared by the steps of:
(1) Dispersing 10-100 parts by weight of cellulose in 5000-50000 parts by weight of deionized water to obtain a solution A containing cellulose;
(2) Adding 100-1000 parts by weight of an amino compound and 100-1000 parts by weight of a cross-linking agent into 5010-50100 parts by weight of a solution A, and adjusting the pH of the solution to 8-10 by adding sodium hydroxide solids to obtain a mixed solution B;
(3) Freezing the mixed solution B obtained in the step (2) for 3-6 hours by a low-temperature directional freezing technology, and then freeze-drying 48 and h to obtain the super-hydrophilic/underwater super-oleophobic cellulose-based porous material.
3. The method for preparing a superhydrophilic/underwater superoleophobic cellulose-based porous material according to claim 1 or claim 2, wherein the cellulose is one of cellulose nanocrystals, filiform cellulose filaments, and lignin cellulose nanofibers.
4. The method for preparing a superhydrophilic/underwater superoleophobic cellulose-based porous material according to claim 1 or claim 2, wherein the amino compound is one of polyethylenimine, polyether ammonia, chitosan, ethylenediamine, glucosamine, isopropanolamine, and butylamine.
5. The method for preparing a superhydrophilic/underwater superoleophobic cellulose-based porous material according to claim 1 or claim 2, wherein the cross-linking agent is one of epichlorohydrin, glutaraldehyde, ethylene glycol diglycidyl ether, 1, 2-epoxyoctadecane, methylenebisacrylamide, and epoxidized soybean oil.
6. The method for preparing a superhydrophilic/underwater superoleophobic cellulose-based porous material according to claim 1 or claim 2, wherein the low-temperature directional freezing technology is adopted, and the freezing temperature is-10 ℃ to-90 ℃.
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