CN111073029A - A kind of preparation method of cellulose nanofibril-based hydrophobic and lipophilic reusable aerogel - Google Patents
A kind of preparation method of cellulose nanofibril-based hydrophobic and lipophilic reusable aerogel Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 33
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- 230000008014 freezing Effects 0.000 claims abstract description 11
- 238000005234 chemical deposition Methods 0.000 claims abstract description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 14
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical group CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 10
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- 238000010521 absorption reaction Methods 0.000 abstract description 12
- 238000011161 development Methods 0.000 abstract description 5
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- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
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- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C08J9/36—After-treatment
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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- 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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- C08J2205/00—Foams characterised by their properties
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Abstract
本发明属于纳米纤维素技术领域，具体公开了一种纤维素纳米纤丝基疏水亲油可重复利用型气凝胶的制备方法。所述包括以下操作步骤：先将用高压微射流制备的CNF分散；然后将分散的CNF悬浊液低温冷冻处理；再将其进行真空冷冻干燥；再使用化学沉积法对CNF气凝胶进行疏水处理，即可得到产品。本发明方法中化学沉积法结合真空冷冻干燥制备纤维素纳米纤丝基疏水亲油可重复利用型气凝胶，该方法将绿色可再生的纤维素制备成可重复利用的疏水亲油气凝胶，更有利于环境的保护以及自然资源的可持续发展。本发明制得的气凝胶吸油倍数高，重复利用后依然有较高的吸油率。
The invention belongs to the technical field of nanocellulose, and specifically discloses a preparation method of a cellulose nanofibril-based hydrophobic and lipophilic reusable aerogel. The process includes the following steps: firstly dispersing the CNF prepared by high-pressure microfluidics; then low-temperature freezing treatment of the dispersed CNF suspension; then vacuum freeze-drying it; and then using chemical deposition method to hydrophobicize the CNF aerogel Processing, you can get the product. In the method of the present invention, chemical deposition method combined with vacuum freeze-drying is used to prepare cellulose nanofibril-based hydrophobic and lipophilic reusable aerogels. The method prepares green renewable cellulose into reusable hydrophobic and oleophilic aerogels. It is more conducive to the protection of the environment and the sustainable development of natural resources. The aerogel prepared by the invention has a high oil absorption ratio, and still has a high oil absorption rate after repeated use.
Description
Technical Field
The invention belongs to the field of lignocellulose materials, and particularly relates to a preparation method of CNF-based hydrophobic oleophilic aerogel.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The rapid development of human economy and science and technology has led to an increasing ecological disruption for mankind in recent decades. Water pollution is now becoming more and more severe, mainly due to petroleum pollution and chemical waste water pollution. Water pollution causes huge damage to the habitat of organisms, causes great economic loss to fishery and tourism, and causes energy crisis. Therefore, oil recovery and water source purification become additionally important.
Cellulose is widely distributed in nature as a high molecular substance, and the nano cellulose aerogel has the advantages of high porosity, high specific surface area and the like, and is particularly suitable to be used as an adsorbent. In the existing methods for preparing nano-cellulose aerogel, in order to keep the uniformity of the aerogel, namely the uniformity of the three-dimensional network structure, the method is mainly adopted by replacing the solvent with lower polarity and then performing vacuum freeze drying, and the risk of chemical pollution is increased, so that the dispersion of the cellulose nano-fibril suspension is relatively ignored. The density of the nano-cellulose aerogel produced at present is as low as 0.001g/cm3It is the lightest solid material in the world. The excellent performance makes it widely used in adsorption separation, heat preservation, medicine release, chemical catalysis and other fields. But its own hydrophilicity of cellulose limits its better application.
Up to now, there have been some reports on methods for preparing superhydrophobic surfaces, such as phase separation, sol-gel, laser or laser chemical etching, etc., and compared with these methods, the chemical vapor deposition method is simple in equipment, convenient to operate and maintain, and can be performed under normal pressure or low vacuum, and can uniformly plate deep holes and fine holes of surfaces or workpieces with complex shapes, and can obtain thin film coatings with high purity, good compactness, small residual stress and good crystallization. Because the reaction gas, the reaction product and the matrix are diffused mutually, a film layer with good adhesive force can be obtained.
Disclosure of Invention
In order to overcome the problems, the invention provides a preparation method of CNF-based hydrophobic oleophilic recyclable aerogel. The method combines a high-pressure micro-jet and chemical vapor deposition method with vacuum freeze drying, and the green renewable cellulose is efficiently utilized to prepare the hydrophobic oleophylic aerogel which can be recycled, so that the method is more favorable for environmental protection and sustainable development of natural resources.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a method of preparing a Cellulose Nanofibril (CNF) based hydrophobic oleophilic reusable aerogel comprising:
uniformly dispersing the CNF suspension, freezing at low temperature, and freeze-drying in vacuum to form CNF aerogel;
and (3) carrying out hydrophobic modification on the CNF aerogel by adopting a chemical deposition method to obtain the cellulose nanofibril-based hydrophobic oleophylic recyclable aerogel.
The product of the invention can be repeatedly utilized on the basis that the raw materials are taken from green renewable resources, and has great practical significance for environmental protection and sustainable development and utilization of resources.
In some embodiments, the CNF suspension is prepared by: cellulose is treated with high pressure homogeneous micro-jets to effectively disperse cellulose nanofibrils.
In some embodiments, the dispersing comprises: emulsification and ultrasonic dispersion. The method can better solve the problems of chemical pollution and dispersion of cellulose nanofibril suspension per se caused by vacuum freeze drying after solvent replacement by adopting the combination of emulsification and ultrasonic dispersion for the pretreatment of a vacuum freeze-dried sample, and also has better preparation of the nano cellulose aerogel on the following hydrophobic treatment
In some embodiments, the rotation speed of the emulsifier is 5000-6000 rpm, and the time is 5-10 min so as to improve the emulsifying effect and efficiency;
in some embodiments, the power of the ultrasound is 200-300W, and the ultrasound time is 5-10 min, so as to improve the dispersion effect of the ultrasound.
In some embodiments, the low-temperature freezing treatment temperature is-30 to-20 ℃ and the time is 12 to 24 hours;
in some embodiments, the vacuum freeze-drying temperature is-60 to-80 ℃ and the time is 36 to 48 hours, so that the CNF suspension subjected to the low-temperature freeze treatment forms aerogel.
In some embodiments, the chemical vapor deposition method is performed at a temperature of 135-155 ℃, a vacuum degree of-15 to-10 bar and a time of 1-2 hours, and the aerogel is subjected to hydrophobic modification, so that the aerogel has good hydrophobic and oleophilic properties.
In some embodiments, the modifier of the chemical vapor deposition process is hexadecyltrimethoxysilane. The research of the application finds that: compared with butanetetracarboxylic acid, palmitic acid, n-octyltriethoxysilane, trimethylchlorosilane and the like, the method has the advantages that the hexadecyl trimethoxysilane (HDTMS) is relatively safe, and when the chemical vapor deposition method is used for preparing the hydrophobic aerogel, the boiling point is lower, so that more HDTMS is volatilized at lower temperature for hydrophobic modification.
In some embodiments, the CNF aerogel is present in a 2: 1-1.2, so that the aerogel obtains a better hydrophobic modification effect.
The invention also provides the Cellulose Nanofibril (CNF) based hydrophobic oleophilic recyclable aerogel prepared by any one of the methods.
The invention also provides application of the Cellulose Nanofibril (CNF) based hydrophobic oleophylic recyclable aerogel in the fields of adsorption separation, heat preservation, drug release and chemical catalysis.
The invention has the beneficial effects that:
(1) the environmental friendliness is improved, the preparation method of the CNF-based hydrophobic oleophylic recyclable aerogel is provided, the environmental protection and the sustainable development of natural resources are facilitated, the oil absorption rate of the product is high, and the product can be recycled.
(2) The operation method is simple, low in cost, universal and easy for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
Fig. 1 is a physical diagram and an SEM diagram of the CNF aerogel prepared in example 1, wherein a is the physical diagram of the CNF aerogel and B is the SEM diagram of the CNF aerogel;
fig. 2 is a physical diagram and a contact angle diagram of the CNF aerogel prepared in example 2, where a is the physical diagram of the CNF aerogel and B is the contact angle diagram of the CNF aerogel.
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 application 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 application. 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.
As described in the background art, the hydrophilicity of the nano-cellulose aerogel itself limits its better application and the complexity of the preparation method. Therefore, the invention provides a method for preparing CNF-based hydrophobic oleophilic aerogel by vacuum freeze drying and chemical vapor deposition, which comprises the following steps:
(1) preparation of CNF: treating cellulose by high-pressure homogenizing microjet to prepare CNF suspension;
(2) dispersion of CNF suspension: firstly, emulsifying the CNF suspension obtained in the step (1) by using an emulsifier, and then dispersing by using ultrasonic waves;
(3) vacuum freeze drying: performing low-temperature freezing treatment on the CNF suspension obtained in the step (2), and then placing the CNF suspension into a vacuum freeze dryer for vacuum freeze drying;
(4) and (3) hydrophobic treatment: performing hydrophobic treatment on the CNF subjected to vacuum freeze drying in the step (3) by using a chemical vapor deposition method by using hexadecyl trimethoxy silane (HDTMS). And obtaining a final product, namely the CNF-based hydrophobic oleophylic recyclable aerogel product.
(5) Adsorption test and recyclability test of CNF aerogel: and (4) adsorbing the engine oil or the soybean oil by the product in the step (4), removing the adsorbed oil after adsorption is finished, and continuously and repeatedly adsorbing the engine oil or the soybean oil.
3 the preferable technical scheme is as follows:
in the step (1), the high-pressure homogenizing micro-jet treatment is carried out for 5-15 times.
In the step (2), the rotating speed of the emulsifier is 5000-6000 rpm, and the time is 5-10 min; the ultrasonic power is 200-300W, and the ultrasonic time is 5-10 min.
In the step (3), the low-temperature freezing treatment temperature is-30 to-20 ℃, and the time is 12 to 24 hours; the temperature of the vacuum freeze drying is-60 to-80 ℃, and the time is 36 to 48 hours.
In the step (4), the temperature of the chemical vapor deposition method is 135-155 ℃, the vacuum degree is-15 to-10 bar, and the time is 1-2 h; mCNF aerogel:MHDTMS＝2:1。
In the step (5), toluene is used for removing oil in the aerogel for 3-5 times, the aerogel is dried in a vacuum drying oven at the temperature of 40-60 ℃ for 24-36 hours, then the oil absorption process is repeated, and the adsorption capacity of the aerogel is tested.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1:
(1) preparation of CNF: performing high-pressure homogenizing micro-jet treatment for 10 times to prepare a CNF suspension;
(2) dispersion of CNF suspension: firstly, emulsifying the CNF suspension obtained in the step (1) by using an emulsifier at a rotating speed of 5500rpm for 8 min; then dispersing by using ultrasonic waves, wherein the power is 250W, and the ultrasonic time is 8 min;
(3) vacuum freeze drying: performing low-temperature freezing treatment on the CNF suspension obtained in the step (2) at the temperature of-25 ℃ for 18 h; then placing the mixture into a vacuum freeze dryer for vacuum freeze drying at the temperature of-70 ℃ for 42 h;
(4) and (3) hydrophobic treatment: performing hydrophobic treatment on the CNF subjected to vacuum freeze drying in the step (3) by using a chemical vapor deposition method by using HDTMS, wherein the temperature of the chemical vapor deposition method is 145 ℃, the vacuum degree is-12.5 bar, and the time is 1.5 h; mCNF aerogel:MHDTMS2: 1. And obtaining a final product, namely the CNF-based hydrophobic oleophylic recyclable aerogel product.
(5) Adsorption test and recyclability test of CNF aerogel: and (3) adsorbing the soybean oil on the product obtained in the step (4), removing the adsorbed oil after adsorption is finished, removing the oil in the aerogel by using toluene for 5 times, drying the aerogel in a vacuum drying oven at 50 ℃ for 32 hours, and continuously and repeatedly adsorbing the engine oil or the soybean oil.
The CNF-based hydrophobic oleophilic reusable aerogel prepared in this example has a specific surface area of: 4.3040m2Per g, contact angle: 145 degrees, and the soybean oil absorption times are as follows: 34.45g/g, the soybean oil absorption times after 5 times of repeated use are as follows: 19.56 g/g.
Example 2:
(1) preparation of CNF: performing high-pressure homogenizing micro-jet treatment for 10 times to prepare a CNF suspension;
(2) dispersion of CNF suspension: firstly, emulsifying the CNF suspension obtained in the step (1) by using an emulsifier at a rotating speed of 5500rpm for 7 min; then dispersing by using ultrasonic waves, wherein the power is 240W, and the ultrasonic time is 7 min;
(3) vacuum freeze drying: performing low-temperature freezing treatment on the CNF suspension obtained in the step (2), wherein the temperature is-22 ℃ and the time is 15 hours; then placing the mixture into a vacuum freeze dryer for vacuum freeze drying at the temperature of-70 ℃ for 39 hours;
(4) and (3) hydrophobic treatment: performing hydrophobic treatment on the CNF subjected to vacuum freeze drying in the step (3) by using a chemical vapor deposition method by using HDTMS, wherein the temperature of the chemical vapor deposition method is 140 ℃, the vacuum degree is-12 bar, and the time is 1.2 h; mCNF aerogel:MHDTMS2: 1. And obtaining a final product, namely the CNF-based hydrophobic oleophylic recyclable aerogel product.
(5) Adsorption test and recyclability test of CNF aerogel: adsorbing the product in the step (4) with machine oil, removing the adsorbed oil after adsorption is finished, removing the oil in the aerogel by using toluene for 5 times, drying the aerogel in a vacuum drying oven at 50 ℃ for 30 hours, and continuously and repeatedly adsorbing the machine oil or the soybean oil.
The CNF-based hydrophobic oleophilic reusable aerogel prepared in this example has a specific surface area of: 4.2940m2Per g, contact angle: 141 DEG, and the oil absorption times are as follows: 26.85g/g, and the oil absorption multiple after 5 times of repeated utilization is as follows: 16.45 g/g.
Example 3:
(1) preparation of CNF: performing high-pressure homogenizing microjet treatment for 5 times to prepare a CNF suspension;
(2) dispersion of CNF suspension: firstly, emulsifying the CNF suspension obtained in the step (1) by using an emulsifier at the rotation speed of 5000rpm for 5 min; then dispersing by using ultrasonic waves, wherein the power is 200W, and the ultrasonic time is 5 min;
(3) vacuum freeze drying: performing low-temperature freezing treatment on the CNF suspension obtained in the step (2) at the temperature of-20 ℃ for 12 hours; then placing the mixture into a vacuum freeze dryer for vacuum freeze drying at the temperature of minus 60 ℃ for 36 hours; obtaining CNF aerogel;
(4) adsorption test and recyclability test of CNF aerogel: adsorbing the product in the step (3) with machine oil, removing the adsorbed oil after adsorption is finished, removing the oil in the aerogel by using toluene for 5 times, drying the aerogel in a vacuum drying oven at 40 ℃ for 24 hours, and continuously and repeatedly adsorbing the machine oil or the soybean oil.
The CNF-based hydrophobic oleophylic reusable aerogel prepared in this embodiment has an oil absorption multiple of: 18.74g/g, and the oil absorption multiple after 5 times of repeated utilization is as follows: 10.83 g/g.
Example 4:
(1) preparation of CNF: performing high-pressure homogenizing microjet treatment for 15 times to prepare a CNF suspension;
(2) dispersion of CNF suspension: firstly, emulsifying the CNF suspension obtained in the step (1) by using an emulsifier at the rotating speed of 6000rpm for 10 min; then dispersing by using ultrasonic waves, wherein the power is 300W, and the ultrasonic time is 10 min;
(3) vacuum freeze drying: performing low-temperature freezing treatment on the CNF suspension obtained in the step (2) at the temperature of minus 30 ℃ for 24 hours; then placing the mixture into a vacuum freeze dryer for vacuum freeze drying at the temperature of 80 ℃ for 48 hours; obtaining CNF aerogel;
(4) adsorption test and recyclability test of CNF aerogel: and (3) adsorbing the soybean oil on the product in the step (3), removing the adsorbed oil after adsorption is finished, removing the oil in the aerogel by using toluene for 5 times, drying the aerogel in a vacuum drying oven at the temperature of 60 ℃ for 36 hours, and continuously and repeatedly adsorbing the engine oil or the soybean oil.
The CNF-based hydrophobic oleophylic reusable aerogel prepared in this embodiment has an oil absorption multiple of: 26.15g/g, and the oil absorption multiple after 5 times of repeated utilization is as follows: 15.57 g/g.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (10)
1. A preparation method of cellulose nanofibril-based hydrophobic oleophilic recyclable aerogel is characterized by comprising the following steps:
uniformly dispersing the CNF suspension, freezing at low temperature, and freeze-drying in vacuum to form CNF aerogel;
and (3) carrying out hydrophobic modification on the CNF aerogel by adopting a chemical deposition method to obtain the cellulose nanofibril-based hydrophobic oleophylic recyclable aerogel.
2. The method for preparing the cellulose nanofibril-based hydrophobic-oleophilic reusable aerogel according to claim 1, wherein the CNF suspension is prepared by: the cellulose was treated with a high pressure homogenous microjet.
3. The method of preparing a cellulose nanofibrillar-based hydrophobic oleophilic reusable aerogel according to claim 1, wherein the dispersing comprises: emulsification and ultrasonic dispersion.
4. The preparation method of the cellulose nanofibril-based hydrophobic-oleophilic reusable aerogel according to claim 1, wherein the rotation speed of the emulsifier is 5000-6000 rpm, and the time is 5-10 min;
or the ultrasonic power is 200-300W, and the ultrasonic time is 5-10 min.
5. The preparation method of the cellulose nanofibril-based hydrophobic-oleophilic reusable aerogel according to claim 1, wherein the low-temperature freezing treatment temperature is-30 to-20 ℃ and the time is 12 to 24 hours;
or the temperature of the vacuum freeze drying is-60 to-80 ℃, and the time is 36 to 48 hours.
6. The preparation method of the cellulose nanofibril-based hydrophobic-oleophilic reusable aerogel according to claim 1, wherein the temperature of the chemical vapor deposition method is 135-155 ℃, the vacuum degree is-15 to-10 bar, and the time is 1-2 h.
7. The method of preparing the cellulose nanofibril-based hydrophobic oleophilic reusable aerogel of claim 1 wherein the chemical vapor deposition modifier is hexadecyltrimethoxysilane.
8. The method of preparing a cellulose nanofibrillar-based hydrophobic oleophilic reusable aerogel according to claim 1, wherein the molar ratio of CNF aerogel to hexadecyltrimethoxysilane is 2:1 to 1.2.
9. A cellulose nanofibril-based hydrophobic oleophilic reusable aerogel prepared by the method of any one of claims 1 to 8.
10. The cellulose nanofibril-based hydrophobic oleophilic reusable aerogel according to claim 9 for use in the fields of adsorptive separation, thermal insulation, drug release, chemical catalysis.
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