CN110128694B - Preparation method of hydrophobic oil-absorption type cellulose-based aerogel - Google Patents
Preparation method of hydrophobic oil-absorption type cellulose-based aerogel Download PDFInfo
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Abstract
The invention relates to the technical field of aerogel materials, and provides a preparation method of a hydrophobic oil-absorbing type cellulose-based aerogel, aiming at solving the problems of poor hydrophobicity, unrecyclable property and low utilization rate of the traditional oil-absorbing material, which comprises the following steps: (1) adding a cross-linking agent into a cellulose nano-fiber aqueous solution, and performing ultrasonic dispersion; (2) pre-freezing, and freeze-drying to obtain aerogel; (3) and (4) carrying out hydrophobic treatment and drying to obtain the hydrophobic oil-absorption type cellulose base aerogel. The invention adopts the bio-based cellulose nano-fiber as the main body of the adsorbent, has wide raw material source and the advantage of biodegradability, is harmless to the environment and conforms to the green development concept; the soaking type hydrophobic treatment is adopted, the method is simple and easy to operate, the prepared cellulose base aerogel is good in hydrophobic oil absorption performance, can be recycled, and is high in resource utilization rate.
Description
Technical Field
The invention relates to the technical field of aerogel materials, in particular to a preparation method of hydrophobic oil-absorption type cellulose-based aerogel.
Background
In recent years, with the development of industrialization, the problem of oil leakage has become prominent, which has become a main source of marine pollution, and marine water pollution has attracted people's attention and movement as one of the most serious environmental problems at present. During the decades of dealing with the problem of oil leakage, various measures have been implemented and perfected, mainly including the most basic treatments of filtration, extraction, and chemical degradation, adsorbent adsorption, etc. Although the methods such as filtration, extraction and the like are simple in experiment, the method wastes time and labor in actual operation and is not high in efficiency; the period required by chemical degradation is long or the added degradation auxiliary agent has certain toxicity, and meanwhile, the chemical degradation is not thorough. The method for adsorbing by the adsorbent has the advantages of simplicity, easiness in operation, high oil absorption efficiency, no toxicity, no harm and the like, and has a wide application prospect.
Although the traditional chemical synthetic adsorbent such as polypropylene fiber, polyurethane foam and other materials have a certain adsorption effect, the traditional chemical synthetic adsorbent is a petroleum-based material and has the defect of non-biodegradability, and another environmental problem can be caused if the traditional chemical synthetic adsorbent is not properly treated after being used. Therefore, the use of bio-based adsorbents is of great significance.
The cellulose aerogel is used as a bio-based material with a large specific surface area and high porosity, and has a good application prospect in the aspect of oil absorption. However, because a large number of hydroxyl groups exist on the surface of the cellulose aerogel, the cellulose aerogel is easy to absorb water while absorbing oil, and even can be well dispersed in an aqueous solution, so that the cellulose aerogel is difficult to clean. In addition, most of the currently used adsorbents are disposable adsorbents, cannot be recycled, and are low in resource utilization rate.
Chinese patent literature discloses a preparation method of a super-hydrophobic oil-absorption nano-cellulose aerogel material, and application publication number is CN107199020A, the super-hydrophobic oil-absorption nano-cellulose aerogel material is prepared by the procedures of preparing nano-cellulose dispersion liquid, preparing composite nano-cellulose, dialyzing, drying and the like, however, the aerogel prepared by the invention is a disposable adsorbent as a large amount of the existing adsorbent, can not be recycled, and has low resource utilization rate.
Disclosure of Invention
The invention provides a preparation method of hydrophobic oil-absorbing type cellulose-based aerogel, aiming at overcoming the problems of poor hydrophobicity, unrecyclability and low utilization rate of the traditional oil-absorbing material, and the preparation method has the advantages of wide raw material source, biodegradability, no harm to the environment and accordance with the green development concept; the prepared cellulose-based aerogel is good in hydrophobic oil absorption performance and can be recycled.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of the hydrophobic oil-absorption type cellulose-based aerogel comprises the following steps:
(1) adding a cross-linking agent into a cellulose nano-fiber aqueous solution, and performing ultrasonic dispersion to obtain a mixed solution;
(2) pre-freezing the mixed solution, and freeze-drying to obtain aerogel; the pre-freezing treatment is used for preventing the mixture from being frozen and crushed (the mixture is frozen by adopting a refrigerator for pre-freezing, the mixture can be directly frozen and cracked due to the freezing of liquid nitrogen, and aerogel can not be formed after the freezing and drying);
(3) and soaking the aerogel in a hydrophobic agent solution for hydrophobic treatment, taking out and drying to obtain the hydrophobic oil-absorption type cellulose base aerogel. The soaking type hydrophobic treatment is adopted, and the method is simple and easy to operate.
Preferably, in the step (1), the concentration of the cellulose nanofiber aqueous solution is 0.5-2 wt%, preferably 1 wt%.
Preferably, in step (1), the crosslinking agent is an epoxy group-, hydroxyl group-, carboxyl group-or isocyanate group-containing compound, such as epichlorohydrin, melamine formaldehyde resin, butanetetracarboxylic acid, diphenylmethane diisocyanate, hexamethylene diisocyanate, etc., preferably butanetetracarboxylic acid.
The basis for screening the cross-linking agent of the invention is: the cellulose nanofiber contains functional groups such as hydroxyl groups and carboxyl groups, the functional groups react with epoxy groups and amino groups more violently, the crosslinking degree is larger, once the crosslinking is excessive, the density of the aerogel is increased, the specific value of oil absorption relative to the aerogel is reduced, and meanwhile, the recovery performance is reduced due to the excessive crosslinking degree, so that the cellulose nanofiber is not favorable for repeated use. The butanetetracarboxylic acid contains carboxyl, the reaction of hydroxyl and carboxyl is mild, and the crosslinking degree is not too high.
Preferably, in the step (1), the solid content ratio of the cellulose nanofibers to the cross-linking agent is (1-40): 1, such as 1/1, 2/1, 4/1, 5/1, 10/1, 10/0.5, 10/0.25, etc., preferably 10/0.5. The solid content ratio of the cellulose nanofibers and the cross-linking agent must be strictly controlled, and if the solid content ratio exceeds the range, the cross-linking degree of the composite is too high, so that the oil absorption effect and the recovery performance are influenced.
Preferably, in the step (1), the ultrasonic power is 100-500W, and the ultrasonic frequency is 20-60 KHz; the ultrasonic temperature is 35-50 ℃, and preferably 40 ℃; the ultrasonic time is 30-120 min, preferably 60-100 min.
Preferably, in the step (2), the pre-freezing treatment is performed by freezing in a refrigerator, the pre-freezing treatment temperature is-18 ℃, and the pre-freezing treatment time is 4-48 h, preferably 12 h; the freeze drying temperature is-76 ℃, and the freeze drying time is 24-72 hours, preferably 36-48 hours.
The pre-freezing treatment adopts refrigerator freezing instead of liquid nitrogen freezing because the pre-freezing treatment has the function of preventing the mixture from being frozen and crushed, but the mixture can be directly frozen and cracked by the freezing of the liquid nitrogen, and the aerogel can not be formed after the freezing and drying.
Preferably, in the step (3), the hydrophobic agent is a silane coupling agent or isocyanate. Such as perfluorosilane coupling agents such as heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, perfluorooctyltrichlorosilane, hexamethylene diisocyanate, diphenylmethane diisocyanate, etc., preferably Hexamethylene Diisocyanate (HDI).
Preferably, in the step (3), the concentration of the hydrophobizing agent solution is 0.1-5 wt%, preferably 1 wt%. The concentration of the hydrophobizing agent solution is controlled within the above range because a certain degree of crosslinking is maintained. The solvent of the hydrophobizing agent solution may be ester, ketone, ether, aromatic hydrocarbon, aliphatic hydrocarbon, benzene, etc., preferably acetone.
Preferably, in the step (3), the hydrophobization treatment temperature is 25-80 ℃, and preferably 60 ℃; the hydrophobization time is 6-12 h, preferably 12 h. The hydrophobization temperature must be strictly controlled within the range defined by the invention, and if the temperature is too low, the reaction rate is slow, and the reaction time is too long; the cellulose nano-fiber is broken and degraded due to the over-high temperature. The hydrophobization treatment time is not easy to be too long, because the too long treatment time can cause the aerogel crosslinking degree to be too large, and the recoverability of the aerogel is influenced.
Preferably, in the step (3), the drying treatment temperature is 60-100 ℃, and preferably 80 ℃; the drying time is 12-48 h, preferably 24 h. Vacuum drying is preferred.
Therefore, the invention has the following beneficial effects: the bio-based cellulose nanofiber is used as the main body of the adsorbent, has the advantages of wide raw material source, biodegradability, no harm to the environment and accordance with the green development concept. The method adopts soaking type hydrophobic treatment, the method is simple and easy to operate, and the prepared cellulose-based aerogel has good hydrophobic oil absorption performance, can be recycled and has high resource utilization rate.
Drawings
Fig. 1 is a digital photograph of a hydrophobic property test of the hydrophobic oil-absorbent type cellulose-based aerogel prepared in example 1.
Fig. 2 is a digital photograph of an oil absorption performance test of the hydrophobic oil-absorbent type cellulose-based aerogel prepared in example 1.
Detailed Description
The technical solution of the present invention is further specifically described below by using specific embodiments and with reference to the accompanying drawings.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
The cellulose nanofiber solutions used in the examples and comparative examples of the present invention were purchased from Zhongshan Nafil New Material Co., Ltd, and manufactured under a batch number of NFC 1802Z.
Example 1
(1) Adding water to a commercially available cellulose nanofiber solution to dilute the solution into a dispersion solution with the concentration of 1 wt%, performing ultrasonic dispersion at 45 ℃ for 9min until cellulose nanofibers are uniformly dispersed in deionized water, adding a cross-linking agent butane tetracarboxylic acid according to the proportion of 10/0.5 of solid content (the dry weight of the cellulose nanofibers/the dry weight of the cross-linking agent is 10/0.5), maintaining the water temperature at 45 ℃, and continuing performing ultrasonic dispersion for 65min until the mixture is uniformly dispersed;
(2) pouring the uniformly dispersed mixture into a specific mould, placing the mould in a refrigerator for pre-freezing at-18 ℃ for about 12 hours, and after pre-freezing and freezing, carrying out freeze drying at-76 ℃ for about 36 hours to obtain the dried cellulose nanofiber crosslinked aerogel;
(3) preparing a 0.2 wt% hexamethylene diisocyanate acetone solution as a hydrophobic treatment agent, soaking the dried cellulose nanofiber crosslinked aerogel in the hydrophobic treatment agent, performing hydrophobic treatment in a water bath at 60 ℃ for 12 hours, taking out the aerogel, and drying in a vacuum oven at 65 ℃ for 20 hours to obtain the hydrophobic oil absorption type cellulose based aerogel.
Fig. 1 is a digital photo of a hydrophobic property test of the hydrophobic oil-absorption type cellulose-based aerogel sample prepared in this embodiment, and as can be seen from fig. 1, the hydrophobic property of the cellulose-based aerogel sample is significant, and even if the sample is immersed in water under the action of a weight, after the load is removed, the sample immediately floats out of the water surface and keeps a floating state on the water surface all the time, which indicates that the composite aerogel after the HDI treatment has excellent hydrophobic property.
Fig. 2 is a digital photo of the oil absorption performance test of the hydrophobic oil absorption type cellulose based aerogel sample prepared by the embodiment, soybean oil is dyed with oil red, and the aerogel is dropped into water and placed in an oil-water mixed solution for the hydrophobic oil absorption performance test. After a period of time, the mixed solution becomes clear and transparent, and the soybean oil is completely adsorbed by the aerogel.
Example 2
(1) Adding water into a commercially available cellulose nanofiber solution to dilute the solution into a dispersion solution with the concentration of 2 wt%, performing ultrasonic dispersion for 10min at the temperature of 35 ℃ until cellulose nanofibers are uniformly dispersed in deionized water, adding a crosslinking agent epichlorohydrin according to the solid content of 5/1 (dry weight of cellulose nanofibers/dry weight of crosslinking agent is 5/1), maintaining the water temperature at 35 ℃, and continuing performing ultrasonic dispersion for 120min until the mixture is uniformly dispersed; the ultrasonic power is 100W, and the ultrasonic frequency is 60 KHz;
(2) pouring the uniformly dispersed mixture into a specific mould (a small glass bottle with the diameter of 1.3 cm), placing the mould in a refrigerator for pre-freezing at-18 ℃ for about 12 hours, and after pre-freezing and freezing, carrying out freeze drying at-76 ℃ for about 36 hours to obtain the dried cellulose nanofiber crosslinked aerogel;
(3) preparing a heptadecafluorodecyl triethoxysilane isopropanol solution with the concentration of 5 wt% as a hydrophobic treatment agent, soaking the dried cellulose nanofiber crosslinked aerogel in the hydrophobic treatment agent, performing hydrophobic treatment in a water bath at 25 ℃ for 12 hours, taking out the aerogel, and drying in a vacuum oven at 100 ℃ for 12 hours to obtain the hydrophobic oil absorption type cellulose base aerogel.
Example 3
(1) Adding water to commercially available cellulose nanofiber solution to dilute the solution into 0.5 wt% dispersion, performing ultrasonic dispersion at 50 ℃ for 5min until cellulose nanofibers are uniformly dispersed in deionized water, adding a cross-linking agent butane tetracarboxylic acid according to a solid content of 10/1 (dry weight of cellulose nanofibers/dry weight of the cross-linking agent is 10/1), maintaining the water temperature at 50 ℃, and continuing ultrasonic dispersion for 30min until the mixture is uniformly dispersed; the ultrasonic power is 500W, and the ultrasonic frequency is 20 KHz;
(2) pouring the uniformly dispersed mixture into a specific mould, placing the mould in a refrigerator for pre-freezing at-18 ℃ for about 12 hours, and after pre-freezing and freezing, carrying out freeze drying at-76 ℃ for about 36 hours to obtain the dried cellulose nanofiber crosslinked aerogel;
(3) preparing a diphenylmethane diisocyanate acetone solution with the concentration of 4 wt% as a hydrophobic treatment agent, soaking the dried cellulose nanofiber crosslinked aerogel in the hydrophobic treatment agent, carrying out hydrophobic treatment in a water bath at 60 ℃ for 12 hours, taking out the aerogel, and drying in a vacuum oven at 60 ℃ for 48 hours to obtain the hydrophobic oil absorption type cellulose based aerogel.
Example 4
(1) Adding water to commercially available cellulose nanofiber solution to dilute the solution into 1 wt% dispersion, performing ultrasonic dispersion at 40 ℃ for 8min until cellulose nanofibers are uniformly dispersed in deionized water, adding a cross-linking agent butane tetracarboxylic acid according to a solid content of 2/1 (dry weight of cellulose nanofibers/dry weight of cross-linking agent is 2/1), maintaining the water temperature at 40 ℃, and continuing ultrasonic dispersion for 70min until the mixture is uniformly dispersed; the ultrasonic power is 200W, and the ultrasonic frequency is 40 KHz;
(2) pouring the uniformly dispersed mixture into a specific mould, pre-freezing the mixture in a refrigerator for about 12 hours, and freeze-drying the mixture at the temperature of minus 76 ℃ for about 36 hours after freezing to obtain the dried cellulose nanofiber crosslinked aerogel;
(3) preparing a Hexamethylene Diisocyanate (HDI) acetone solution with the concentration of 1 wt% as a hydrophobic treatment agent, soaking the dried cellulose nanofiber crosslinked aerogel in the hydrophobic treatment agent, performing hydrophobic treatment in a water bath at 60 ℃ for 12 hours, taking out the aerogel, and drying in a vacuum oven at 80 ℃ for 24 hours to obtain the hydrophobic oil absorption type cellulose base aerogel.
Comparative example 1 (without addition of crosslinking agent)
Comparative example 1 differs from example 1 in that the crosslinker butanetetracarboxylic acid was not added in step (1) and the remaining steps and process conditions were exactly the same.
Comparative example 2 (No crosslinker added, No hydrophobic treatment)
Comparative example 2 differs from example 1 in that the crosslinker butanetetracarboxylic acid was not added in step (1), step (3) was not present, and the remaining steps and process conditions were exactly the same.
The performance indexes of the hydrophobic oil-absorbent type cellulose-based aerogels of examples 1 to 4 and the aerogels of comparative examples 1 to 2 were examined, and the results are shown in tables 1 and 2:
TABLE 1 measurement results of mechanical properties of aerogels of examples 1 to 4 and comparative examples 1 to 2
| Numbering | Compression ratio (%) | Compression rebound resilience (%) |
| Example 1 | 64.1 | 68.5 |
| Example 2 | 67.5 | 74.4 |
| Example 3 | 68.9 | 71.2 |
| Example 4 | 70.6 | 86.6 |
| Comparative example 1 | 73.4 | 50.3 |
| Comparative example 2 | 78.3 | 23.2 |
Mechanical property tests were performed on the samples of examples 1 to 4 of the present invention and comparative examples 1 to 2, and the test results are shown in table 1. A 500g weight was placed on top of the aerogel and the compression and rebound after unloading of the aerogel were tested. As can be seen from Table 1, the pure cellulose nanofiber aerogel has extremely poor recovery performance, and the compression recovery performance of the aerogel can be obviously improved after the cross-linking agent is added, so that the method has important significance on the recycling of the composite aerogel.
TABLE 2 measurement results of hydrophobic oil absorption Properties of aerogels of examples 1 to 4 and comparative examples 1 to 2
| Numbering | Density (kg/m)3) | Soybean oil (g/g) | Liquid paraffin (g/g) |
| Example 1 | 12.3 | 73.5 | 86.8 |
| Example 2 | 13.4 | 70.7 | 83.1 |
| Example 3 | 12.9 | 72.9 | 84.5 |
| Example 4 | 16.1 | 65.3 | 69.9 |
| Comparative example 1 | 11.6 | 60.7 | 78.3 |
| Comparative example 2 | 7.9 | 30.4 | 35.2 |
The samples of examples 1 to 4 and comparative examples 1 to 2 of the present invention were subjected to a hydrophobic oil absorption performance test, that is, the mass of oil absorbed by a unit mass of aerogel in an oil-water mixed solution was measured, and the test results are shown in table 2. The aerogel treated by the hydrophobing agent can adsorb soybean oil which is about 70 times of the self weight of the aerogel and liquid paraffin which is about 80 times of the self weight of the aerogel, and the oil absorption effect is obvious. And for pure cellulose aerogel, the water-absorbing cellulose aerogel can absorb water while absorbing oil, and the water-absorbing effect is better than the oil-absorbing effect.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (2)
1. The preparation method of the hydrophobic oil-absorption type cellulose-based aerogel is characterized by comprising the following steps of:
(1) adding a cross-linking agent into a cellulose nano-fiber aqueous solution, and performing ultrasonic dispersion to obtain a mixed solution;
wherein the concentration of the cellulose nanofiber aqueous solution is 0.5-2 wt%;
the cross-linking agent is butane tetracarboxylic acid;
the solid content ratio of the cellulose nano-fiber to the cross-linking agent is 10: 0.5;
the ultrasonic temperature is 35-50 ℃; the ultrasonic time is 30-120 min;
(2) pre-freezing the mixed solution, and freeze-drying to obtain aerogel;
wherein the pre-freezing treatment temperature is-18 ℃, and the pre-freezing treatment time is 4-48 h; the freeze drying temperature is-76 ℃, and the freeze drying time is 24-72 hours;
(3) soaking the aerogel in a hydrophobic agent solution for hydrophobic treatment, taking out and drying to obtain the hydrophobic oil absorption type cellulose base aerogel;
wherein the concentration of the hydrophobing agent solution is 0.1-5 wt%;
the hydrophobization treatment temperature is 25-80 ℃; the hydrophobization treatment time is 6-12 h;
the drying temperature is 60-100 ℃; the drying time is 12-48 h.
2. The method for preparing a hydrophobic oil-absorption type cellulose-based aerogel according to claim 1, wherein in the step (3), the hydrophobic agent is a silane coupling agent or isocyanate.
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