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CN116693704B - Preparation method of cellulose nanocrystalline based on tobacco waste - Google Patents

Preparation method of cellulose nanocrystalline based on tobacco waste Download PDF

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CN116693704B
CN116693704B CN202310758383.8A CN202310758383A CN116693704B CN 116693704 B CN116693704 B CN 116693704B CN 202310758383 A CN202310758383 A CN 202310758383A CN 116693704 B CN116693704 B CN 116693704B
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cellulose
sulfuric acid
tobacco waste
eutectic solvent
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CN116693704A (en
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陈丽娟
宋祖国
杨建礼
吴成春
刘振宇
姚思愚
葛畅
左满兴
张二强
潘广乐
赵敏
胡慧博
石栋栋
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Zhengzhou University of Light Industry
China Tobacco Shaanxi Industrial Co Ltd
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China Tobacco Shaanxi Industrial Co Ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/003Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids

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Abstract

本发明提出了一种基于烟草废弃物的纤维素纳米晶的制备方法,属于纳米晶纤维素制备的技术领域,用以解决纳米晶纤维素制备中硫酸用量大、热稳定性差的技术问题。本发明包括以下步骤:(1)提取烟草废弃物中的纤维素;(2)将纤维素在硫酸‑低共熔溶剂耦合溶液中溶胀酸解,得到纳米晶纤维素悬浊液,将纳米晶纤维素悬浊液离心分离、透析、干燥得到纳米晶纤维素;所述硫酸‑低共熔溶剂耦合溶液包括硫酸溶液和低共熔溶剂;所述低共熔溶剂包括有机酸和多元醇。采用硫酸‑低共熔溶剂耦合水解纤维素制备纳米晶纤维素,通过加入低共熔溶剂降低硫酸用量,并且所制备纳米晶纤维素热分解温度高,稳定性好。

The present invention proposes a method for preparing cellulose nanocrystals based on tobacco waste, which belongs to the technical field of nanocrystalline cellulose preparation and is used to solve the technical problems of large amount of sulfuric acid and poor thermal stability in the preparation of nanocrystalline cellulose. The present invention comprises the following steps: (1) extracting cellulose from tobacco waste; (2) swelling and acidifying cellulose in a sulfuric acid-low eutectic solvent coupling solution to obtain a nanocrystalline cellulose suspension, centrifuging, dialysing and drying the nanocrystalline cellulose suspension to obtain nanocrystalline cellulose; the sulfuric acid-low eutectic solvent coupling solution comprises a sulfuric acid solution and a low eutectic solvent; the low eutectic solvent comprises an organic acid and a polyol. Nanocrystalline cellulose is prepared by coupling cellulose hydrolysis with sulfuric acid-low eutectic solvent, and the amount of sulfuric acid is reduced by adding a low eutectic solvent, and the prepared nanocrystalline cellulose has a high thermal decomposition temperature and good stability.

Description

一种基于烟草废弃物的纤维素纳米晶的制备方法A method for preparing cellulose nanocrystals based on tobacco waste

技术领域Technical Field

本发明属于纳米晶纤维素制备的技术领域,尤其涉及一种基于烟草废弃物的纤维素纳米晶的制备方法。The invention belongs to the technical field of nanocrystalline cellulose preparation, and in particular relates to a method for preparing cellulose nanocrystals based on tobacco waste.

背景技术Background Art

我国是烟草种植大国,每年烟叶产量约300万吨,其中约有25%-30%的烟叶、烟末等下脚料不能用于卷烟生产,估计全国烟草废弃物的总量在150万吨以上。烟草废弃物中约含有丰富的纤维素,粗纤维含量基本在35%左右。若对这些废弃物进行合理利用,不仅可以获得符合绿色卫生标准的天然化工原料,也可以减轻烟草废弃物带来的土质和土壤结构的改变,避免有害成分的污染。因此,合理开发利用烟草废弃物这一丰富的副产品资源,使之变废为宝,可产生巨大的经济效益和良好的社会效益与环境效益。my country is a major tobacco-growing country, with an annual tobacco leaf output of about 3 million tons, of which about 25%-30% of tobacco leaves, tobacco dust and other waste materials cannot be used for cigarette production. It is estimated that the total amount of tobacco waste in the country is more than 1.5 million tons. Tobacco waste contains rich cellulose, and the crude fiber content is basically around 35%. If these wastes are used reasonably, not only can natural chemical raw materials that meet green hygiene standards be obtained, but also the changes in soil quality and soil structure caused by tobacco waste can be reduced, and pollution of harmful components can be avoided. Therefore, the rational development and utilization of tobacco waste, a rich by-product resource, can turn waste into treasure, which can produce huge economic benefits and good social and environmental benefits.

纤维素是世界上最丰富、来源分布最广泛的可再生生物资源,成本低、生物性能良好,但由于其本身结构紧密,分子间存在氢键,不溶于大多数溶剂,导致其无法很好地被利用。纤维素经过化学、物理、生物等方法将某一维度上的尺寸减小到纳米级别纤维素,尺寸不超过几微米,同时兼具纳米材料的理化特性和纤维素材料的生理特性,具有大比表面积、高强度、大长径比等优良特性,在复合材料、生物医药、食品、化工等领域具有较高的应用价值。Cellulose is the most abundant and widely distributed renewable biological resource in the world. It has low cost and good biological properties. However, due to its compact structure, hydrogen bonds between molecules, and insolubility in most solvents, it cannot be well utilized. Cellulose is reduced to nanoscale cellulose by chemical, physical, and biological methods. The size does not exceed a few microns. It has both the physical and chemical properties of nanomaterials and the physiological properties of cellulose materials. It has excellent properties such as large specific surface area, high strength, and large aspect ratio. It has high application value in composite materials, biomedicine, food, and chemical industries.

根据纳米纤维素的形态,可分为以下四类:晶体形纳米纤维素(纳米晶纤维素,CNC)、纤丝状纳米纤维素(纤维素纳米纤丝,CNF)、球形纳米纤维素和片状纳米纤维素。纳米晶纤维素(CNC)主要制备方法为纤维素分子经过化学(酸、离子液体等)、物理、生物方法(酶催化法)降解其中的非结晶区,将结晶区保留下来的短棒状或者针状的晶体物质。单一硫酸酸解法是最常用的方法,但在制备过程中需使用大量的浓硫酸,且存在酸回收困难、腐蚀设备等问题。例如专利公开号CN108299563A一种硫酸催化有机酸水解制备球形纤维素纳米晶的方法,采用无水草酸或马来酸与浓硫酸混合的方式提取纤维素纳米晶,但是,该工艺仍然需要采用浓硫酸。再者,专利公开号CN 111548426A与CN 112010985A分别公开了采用二水合草酸和氯化胆碱、柠檬酸和甜菜碱混合制备低共熔溶剂,低共熔溶剂与浓硫酸混合制备纤维素纳米晶体,但是,采用上述两种低共熔溶剂所制备纤维素纳米晶体的热解温度低,热稳定性较差。According to the morphology of nanocellulose, it can be divided into the following four categories: crystalline nanocellulose (nanocrystalline cellulose, CNC), fibrillar nanocellulose (cellulose nanofibrils, CNF), spherical nanocellulose and sheet nanocellulose. The main preparation method of nanocrystalline cellulose (CNC) is to degrade the non-crystalline region of cellulose molecules through chemical (acid, ionic liquid, etc.), physical, and biological methods (enzyme catalysis), and retain the short rod-shaped or needle-shaped crystalline substances in the crystalline region. The single sulfuric acid acid hydrolysis method is the most commonly used method, but a large amount of concentrated sulfuric acid needs to be used in the preparation process, and there are problems such as acid recovery difficulties and corrosion equipment. For example, patent publication number CN108299563A is a method for preparing spherical cellulose nanocrystals by sulfuric acid-catalyzed organic acid hydrolysis, which uses anhydrous oxalic acid or maleic acid mixed with concentrated sulfuric acid to extract cellulose nanocrystals, but the process still needs to use concentrated sulfuric acid. Furthermore, patent publication numbers CN 111548426A and CN 112010985A disclose respectively the use of oxalic acid dihydrate and choline chloride, citric acid and betaine to mix to prepare a low eutectic solvent, and the use of a low eutectic solvent and concentrated sulfuric acid to mix to prepare cellulose nanocrystals. However, the cellulose nanocrystals prepared by using the above two low eutectic solvents have a low pyrolysis temperature and poor thermal stability.

发明内容Summary of the invention

针对纳米晶纤维素制备中硫酸用量大、热稳定性差的技术问题,本发明提出一种基于烟草废弃物的纤维素纳米晶的制备方法,采用硫酸-低共熔溶剂耦合水解纤维素制备纳米晶纤维素,通过加入低共熔溶剂降低硫酸用量,并且纳米晶纤维素热分解温度高,稳定性好。In view of the technical problems of large amount of sulfuric acid used and poor thermal stability in the preparation of nanocrystalline cellulose, the present invention proposes a method for preparing cellulose nanocrystals based on tobacco waste, wherein nanocrystalline cellulose is prepared by coupling hydrolysis of cellulose with sulfuric acid and a low eutectic solvent, and the amount of sulfuric acid is reduced by adding a low eutectic solvent. In addition, the nanocrystalline cellulose has a high thermal decomposition temperature and good stability.

为了达到上述目的,本发明的技术方案是这样实现的:In order to achieve the above object, the technical solution of the present invention is achieved as follows:

一种基于烟草废弃物的纤维素纳米晶的制备方法,包括以下步骤:A method for preparing cellulose nanocrystals based on tobacco waste comprises the following steps:

提取烟草废弃物中的纤维素;Extraction of cellulose from tobacco waste;

将纤维素在硫酸-低共熔溶剂耦合溶液中溶胀酸解,得到纳米晶纤维素悬浊液,将纳米晶纤维素悬浊液离心分离、透析、干燥得到纳米晶纤维素;The cellulose is swelled and acid-lyzed in a sulfuric acid-deep eutectic solvent coupling solution to obtain a nanocrystalline cellulose suspension, and the nanocrystalline cellulose suspension is centrifuged, dialyzed, and dried to obtain nanocrystalline cellulose;

所述硫酸-低共熔溶剂耦合溶液包括硫酸溶液和低共熔溶剂。The sulfuric acid-deep eutectic solvent coupling solution comprises a sulfuric acid solution and a deep eutectic solvent.

所述纤维素与硫酸-低共熔溶剂耦合溶液的料液比为1:(5-10)g/mL。The solid-liquid ratio of the cellulose to the sulfuric acid-low eutectic solvent coupling solution is 1:(5-10) g/mL.

所述低共熔溶剂包括有机酸和多元醇,有机酸和多元醇的质量比为1:(1-4)。The low eutectic solvent comprises an organic acid and a polyol, and the mass ratio of the organic acid to the polyol is 1:(1-4).

所述有机酸为草酸、乳酸或马来酸中的任意一种或两种以上,此外还可以为其他类型的多元羧酸;所述多元醇为丙三醇或乙二醇。The organic acid is any one or more of oxalic acid, lactic acid or maleic acid, and may also be other types of polycarboxylic acids; the polyol is glycerol or ethylene glycol.

所述硫酸溶液与低共熔溶剂的质量比为1:(0.25-3)。The mass ratio of the sulfuric acid solution to the low eutectic solvent is 1:(0.25-3).

所述硫酸溶液的浓度为25-35wt%。The concentration of the sulfuric acid solution is 25-35 wt %.

所述溶胀酸解的温度为80-100℃,时间为3-5h。The swelling acid hydrolysis temperature is 80-100° C. and the time is 3-5 hours.

所述步骤(1)中提取烟草废弃物中的纤维素的方法为:将烟草废弃物粉末与NaOH溶液搅拌混匀,高温回流,加入H2O2溶液,经过分离、洗涤、干燥后获得纤维素。The method for extracting cellulose from tobacco waste in step (1) is as follows: tobacco waste powder is stirred and mixed with NaOH solution, refluxed at high temperature, H2O2 solution is added, and cellulose is obtained after separation, washing and drying.

所述烟草废弃物粉末与NaOH溶液的料液比为1:(8-20)g/mL;所述烟草废弃物粉末粒度为100-200目,NaOH溶液的浓度为1-5wt%。The material-liquid ratio of the tobacco waste powder to the NaOH solution is 1:(8-20) g/mL; the particle size of the tobacco waste powder is 100-200 meshes, and the concentration of the NaOH solution is 1-5wt%.

所述高温回流的温度为70-100℃,时间为60-90min;高温回流后的溶液温度为50-80℃时加入浓度为3-30wt%的H2O2溶液,保持此温度30-90min,烟草废弃物粉末与H2O2溶液的料液为1:(0.5-2)g/mL。The high temperature reflux temperature is 70-100°C, and the time is 60-90min. When the solution temperature after high temperature reflux is 50-80°C, add H2O2 solution with a concentration of 3-30wt %, and keep this temperature for 30-90min. The feed liquid ratio of tobacco waste powder and H2O2 solution is 1: (0.5-2) g/mL.

本发明的有益效果:本发明的制备纤维素纳米晶体方法,反应条件比较温和,所制备纤维素纳米晶的热解温度为379℃,更为稳定,单独多元醇可使纤维素充分溶胀,当多元醇和羧酸组成低共熔溶剂时,使纤维素溶胀更充分,获得的纳米晶纤维素结晶度更高,因而更稳定。在制备过程中通过NaOH溶液和H2O2除去烟草废弃物中的杂质和木质素,所得的产物经膜透析处理纯度更高。本发明在制备的过程中采用稀硫酸,通过低共熔溶剂降低了硫酸的使用量,使制备过程更为安全,同时又能提高纤维素纳米晶的得率。Beneficial effects of the present invention: The method for preparing cellulose nanocrystals of the present invention has relatively mild reaction conditions, and the pyrolysis temperature of the prepared cellulose nanocrystals is 379°C, which is more stable. The polyol alone can fully swell the cellulose, and when the polyol and carboxylic acid form a low eutectic solvent, the cellulose swells more fully, and the obtained nanocrystalline cellulose has a higher crystallinity and is therefore more stable. In the preparation process, impurities and lignin in tobacco waste are removed by NaOH solution and H2O2 , and the obtained product has a higher purity after membrane dialysis treatment. In the preparation process of the present invention, dilute sulfuric acid is used, and the use of sulfuric acid is reduced by a low eutectic solvent, making the preparation process safer and at the same time improving the yield of cellulose nanocrystals.

本发明以烟草废弃物为原料,变废为宝,提供了一种环保、有效和工艺简单的制备方法,得到的纤维素纳米晶形态疏松、结晶度高和热性能良好。The invention uses tobacco waste as raw material, turns waste into treasure, and provides an environmentally friendly, effective and simple preparation method. The obtained cellulose nanocrystals have loose morphology, high crystallinity and good thermal properties.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

图1为本发明实施例3获得的纳米晶纤维素的扫描电镜(SEM)图。FIG1 is a scanning electron microscope (SEM) image of nanocrystalline cellulose obtained in Example 3 of the present invention.

图2为本发明实施例3获得的纳米晶纤维素的X射线衍射(XRD)图。FIG. 2 is an X-ray diffraction (XRD) diagram of nanocrystalline cellulose obtained in Example 3 of the present invention.

图3为本发明实施例3获得的纳米晶纤维素的热解(TG)图。FIG3 is a thermal decomposition (TG) diagram of nanocrystalline cellulose obtained in Example 3 of the present invention.

具体实施方式DETAILED DESCRIPTION

下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

烟草废弃物制备的纳米晶纤维素得率Yield of Nanocrystalline Cellulose Prepared from Tobacco Waste

利用下列公式计算得率:The yield is calculated using the following formula:

得率=(m2/m1)*100%Yield = (m2/m1)*100%

式中:m1为烟草废弃物粉末质量,m2为干燥后纳米晶纤维素质量。Where: m1 is the mass of tobacco waste powder, and m2 is the mass of nanocrystalline cellulose after drying.

实施例1Example 1

一种基于烟草废弃物的纳米晶纤维素的制备方法,包括以下步骤:A method for preparing nanocrystalline cellulose based on tobacco waste comprises the following steps:

取100g 100目的烟草废弃物粉末,加入800mL 5wt%的NaOH溶液,在70℃温度下提取60min然后,加入50mL 5wt%H2O2,继续回流1h,离心去除上清液,去离子水洗至中性,冷冻真空干燥,得到纤维素。Take 100g 100-mesh tobacco waste powder, add 800mL 5wt% NaOH solution, extract at 70℃ for 60min, then add 50mL 5wt% H 2 O 2 , continue to reflux for 1h, centrifuge to remove supernatant, wash with deionized water until neutral, freeze-dry in vacuum to obtain cellulose.

称取纤维素10g,按照料液比1:5,加入50mL硫酸-低共熔溶剂耦合溶液,在80℃下催化水解3h,加入去离子水混合后离心,反复操作3次,然后采用截留分子量≥2000Da的透析袋进行透析,直至纳米晶纤维素悬浊液的pH值约为7,在8000r/min的转速下离心10min,真空冷冻干燥获得纳米晶纤维素。硫酸-低共熔溶剂耦合溶液配制方法为:草酸与丙三醇按照质量比1:1混合,放入超声波中加热超声30min,然后25wt%硫酸与其按照比例为1:0.25混合,即制得硫酸-低共熔溶剂。Weigh 10g of cellulose, add 50mL of sulfuric acid-deep eutectic solvent coupling solution according to a solid-liquid ratio of 1:5, catalytically hydrolyze at 80°C for 3h, add deionized water and mix, centrifuge, repeat the operation 3 times, and then dialyze using a dialysis bag with a molecular weight cutoff of ≥2000Da until the pH value of the nanocrystalline cellulose suspension is about 7, centrifuge at a speed of 8000r/min for 10min, and vacuum freeze-dry to obtain nanocrystalline cellulose. The sulfuric acid-deep eutectic solvent coupling solution is prepared by mixing oxalic acid and glycerol in a mass ratio of 1:1, placing them in an ultrasonic wave for heating and ultrasonication for 30min, and then mixing 25wt% sulfuric acid with them in a ratio of 1:0.25 to obtain a sulfuric acid-deep eutectic solvent.

本实施例的纳米晶纤维素得率为26.5%。The yield of nanocrystalline cellulose in this example is 26.5%.

实施例2Example 2

一种基于烟草废弃物的纳米晶纤维素的制备方法,包括以下步骤:A method for preparing nanocrystalline cellulose based on tobacco waste comprises the following steps:

取100g 200目的烟草废弃物粉末,加入1500mL 5wt%的NaOH溶液,在85℃温度下提取60min然后,加入100mL 5wt%H2O2,继续回流1h,离心去除上清液,去离子水洗至中性,冷冻真空干燥,得到纤维素。Take 100g 200-mesh tobacco waste powder, add 1500mL 5wt% NaOH solution, extract at 85℃ for 60min, then add 100mL 5wt% H 2 O 2 , continue to reflux for 1h, centrifuge to remove supernatant, wash with deionized water to neutrality, freeze-dry in vacuum to obtain cellulose.

称取纤维素10g,按照料液比1:8,加入80mL硫酸-低共熔溶剂耦合溶液,在90℃下催化水解3h,加入去离子水混合后离心,反复操作3次,然后采用截留分子量≥2000Da的透析袋进行透析,直至纳米晶纤维素悬浊液的pH值约为7,在8000r/min的转速下离心10min,真空冷冻干燥获得纳米晶纤维素。硫酸-低共熔溶剂耦合溶液配制方法为:草酸与丙三醇按照质量比1:2混合,放入超声波中加热超声30min,然后30wt%硫酸与其按照比例为1:1混合,即制得硫酸-低共熔溶剂。Weigh 10g of cellulose, add 80mL of sulfuric acid-deep eutectic solvent coupling solution according to the solid-liquid ratio of 1:8, catalytically hydrolyze at 90°C for 3h, add deionized water and mix, centrifuge, repeat the operation 3 times, and then dialyze with a dialysis bag with a molecular weight cutoff of ≥2000Da until the pH value of the nanocrystalline cellulose suspension is about 7, centrifuge at a speed of 8000r/min for 10min, and vacuum freeze-dry to obtain nanocrystalline cellulose. The preparation method of sulfuric acid-deep eutectic solvent coupling solution is: oxalic acid and glycerol are mixed in a mass ratio of 1:2, placed in an ultrasonic wave for heating and ultrasonication for 30min, and then 30wt% sulfuric acid is mixed with it in a ratio of 1:1 to obtain sulfuric acid-deep eutectic solvent.

本实施例的纳米晶纤维素得率为28.1%。The yield of nanocrystalline cellulose in this example is 28.1%.

实施例3Example 3

一种基于烟草废弃物的纳米晶纤维素的制备方法,包括以下步骤:A method for preparing nanocrystalline cellulose based on tobacco waste comprises the following steps:

取100g 150目的烟草废弃物粉末,加入2000mL 5wt%的NaOH溶液,在80℃温度下提取60min然后,加入100mL 5wt%H2O2,继续回流1h,离心去除上清液,去离子水洗至中性,冷冻真空干燥,得到纤维素。Take 100g 150 mesh tobacco waste powder, add 2000mL 5wt% NaOH solution, extract at 80℃ for 60min, then add 100mL 5wt% H2O2 , continue to reflux for 1h, centrifuge to remove supernatant, wash with deionized water to neutrality, freeze-dry in vacuum to obtain cellulose.

称取纤维素10g,按照料液比1:8,加入80mL硫酸-低共熔溶剂耦合溶液,在90℃下催化水解4h,加入去离子水混合后离心,反复操作5次,然后采用截留分子量≥2000Da的透析袋透析,直至纳米晶纤维素悬浊液的pH值约为7,在8000r/min的转速下离心10min,真空冷冻干燥获得纳米晶纤维素。硫酸-低共熔溶剂耦合溶液配制方法为:草酸与丙三醇按照质量比1:4混合,放入超声波中加热超声30min,然后35wt%硫酸与其按照比例为1:3混合,即制得硫酸-低共熔溶剂,即制得硫酸-低共熔溶剂。Weigh 10g of cellulose, add 80mL of sulfuric acid-low eutectic solvent coupling solution according to the solid-liquid ratio of 1:8, catalytically hydrolyze at 90°C for 4h, add deionized water and mix, centrifuge, repeat the operation 5 times, and then dialyze with a dialysis bag with a molecular weight cutoff of ≥2000Da until the pH value of the nanocrystalline cellulose suspension is about 7, centrifuge at a speed of 8000r/min for 10min, and vacuum freeze-dry to obtain nanocrystalline cellulose. The preparation method of sulfuric acid-low eutectic solvent coupling solution is: oxalic acid and glycerol are mixed in a mass ratio of 1:4, placed in an ultrasonic wave for heating and ultrasonication for 30min, and then 35wt% sulfuric acid is mixed with it in a ratio of 1:3 to obtain sulfuric acid-low eutectic solvent.

本实施例的纳米晶纤维素得率为29.5%。The yield of nanocrystalline cellulose in this example is 29.5%.

对本实施例所制备纳米晶纤维素进行表征,图1为纳米晶纤维素的SEM图,由图1可知纤维素纳米晶整体呈杂乱的分散片状结构,表面疏松,有较多的孔洞和塌陷;The nanocrystalline cellulose prepared in this example was characterized. FIG1 is a SEM image of the nanocrystalline cellulose. FIG1 shows that the cellulose nanocrystals are in a disordered dispersed sheet structure as a whole, with a loose surface and many holes and collapses.

图2为纳米晶纤维素的XRD图,由图2可知纳米晶纤维素在2θ=13°、22.5°、35.5°有明显的衍射峰,结晶度较高。FIG2 is an XRD diagram of nanocrystalline cellulose. It can be seen from FIG2 that nanocrystalline cellulose has obvious diffraction peaks at 2θ=13°, 22.5°, and 35.5°, and has a high degree of crystallinity.

图3为纳米晶纤维素的TG图,从图3中可以看出,开始出现裂解尖峰的温度379℃。FIG3 is a TG graph of nanocrystalline cellulose. It can be seen from FIG3 that the temperature at which the pyrolysis peak begins to appear is 379° C.

实施例4Example 4

一种基于烟草废弃物的纳米晶纤维素的制备方法,包括以下步骤:A method for preparing nanocrystalline cellulose based on tobacco waste comprises the following steps:

取100g 100目的烟草废弃物粉末,加入2000mL 5wt%的NaOH溶液,在70℃温度下提取70min然后,加入100mL 5wt%H2O2,继续回流90min,离心去除上清液,去离子水洗至中性,冷冻真空干燥,得到纤维素。Take 100g 100-mesh tobacco waste powder, add 2000mL 5wt% NaOH solution, extract at 70℃ for 70min, then add 100mL 5wt% H 2 O 2 , continue to reflux for 90min, centrifuge to remove supernatant, wash with deionized water to neutrality, freeze-dry in vacuum to obtain cellulose.

称取纤维素10g,按照料液比1:10,加入100mL硫酸-低共熔溶剂耦合溶液,在80℃下催化水解3h,加入去离子水混合后离心,反复操作3次,然后采用截留分子量≥2000Da的透析袋透析,直至纳米晶纤维素悬浊液的pH值约为7,在8000r/min的转速下离心10min,真空冷冻干燥获得纳米晶纤维素。硫酸-低共熔溶剂耦合溶液配制方法为:草酸、乳酸与丙三醇按照质量比0.5:0.5:1混合,放入超声波中加热超声30min,然后35wt%硫酸与其按照比例为1:3混合,即制得硫酸-低共熔溶剂,即制得硫酸-低共熔溶剂。Weigh 10g of cellulose, add 100mL of sulfuric acid-deep eutectic solvent coupling solution according to a solid-liquid ratio of 1:10, catalytically hydrolyze at 80°C for 3h, add deionized water and mix, centrifuge, repeat the operation 3 times, and then dialyze with a dialysis bag with a molecular weight cutoff of ≥2000Da until the pH value of the nanocrystalline cellulose suspension is about 7, centrifuge at a speed of 8000r/min for 10min, and vacuum freeze-dry to obtain nanocrystalline cellulose. The preparation method of sulfuric acid-deep eutectic solvent coupling solution is: oxalic acid, lactic acid and glycerol are mixed in a mass ratio of 0.5:0.5:1, placed in an ultrasonic wave for heating and ultrasonication for 30min, and then 35wt% sulfuric acid is mixed with it in a ratio of 1:3 to obtain sulfuric acid-deep eutectic solvent, that is, sulfuric acid-deep eutectic solvent is obtained.

本实施例的纳米晶纤维素的得率为28.5%。The yield of nanocrystalline cellulose in this example is 28.5%.

实施例5Example 5

一种基于烟草废弃物的纳米晶纤维素的制备方法,包括以下步骤:A method for preparing nanocrystalline cellulose based on tobacco waste comprises the following steps:

取100g 200目的烟草废弃物粉末,加入1500mL 5wt%的NaOH溶液,在90℃温度下提取60min然后,加入100mL 5wt%H2O2,继续回流1h,离心去除上清液,去离子水洗至中性,冷冻真空干燥,得到纤维素。Take 100g 200-mesh tobacco waste powder, add 1500mL 5wt% NaOH solution, extract at 90℃ for 60min, then add 100mL 5wt% H 2 O 2 , continue to reflux for 1h, centrifuge to remove supernatant, wash with deionized water to neutrality, freeze-dry in vacuum to obtain cellulose.

称取纤维素10g,按照料液比1:10,加入100mL硫酸-低共熔溶剂耦合溶液,在100℃下催化水解5h,加入去离子水混合后离心,反复操作4次,然后采用截留分子量≥2000Da的透析袋透析,直至纳米晶纤维素悬浊液的pH值约为7,在8000r/min的转速下离心10min,真空冷冻干燥获得纳米晶纤维素。硫酸-低共熔溶剂耦合溶液配制方法为:草酸、乳酸与丙三醇按照质量比1:1:4混合,放入超声波中加热超声30min,然后35wt%硫酸与其按照比例为1:3混合,即制得硫酸-低共熔溶剂,即制得硫酸-低共熔溶剂。Weigh 10g of cellulose, add 100mL of sulfuric acid-deep eutectic solvent coupling solution according to a solid-liquid ratio of 1:10, catalytically hydrolyze at 100°C for 5h, add deionized water and mix, centrifuge, repeat the operation 4 times, and then dialyze with a dialysis bag with a molecular weight cutoff of ≥2000Da until the pH value of the nanocrystalline cellulose suspension is about 7, centrifuge at a speed of 8000r/min for 10min, and vacuum freeze-dry to obtain nanocrystalline cellulose. The preparation method of sulfuric acid-deep eutectic solvent coupling solution is: oxalic acid, lactic acid and glycerol are mixed in a mass ratio of 1:1:4, placed in an ultrasonic wave for heating and ultrasonication for 30min, and then 35wt% sulfuric acid is mixed with it in a ratio of 1:3 to obtain a sulfuric acid-deep eutectic solvent.

本实施例的纳米晶纤维素的得率为29.1%。The yield of nanocrystalline cellulose in this example is 29.1%.

实施例6Example 6

一种基于烟草废弃物的纳米晶纤维素的制备方法,包括以下步骤:A method for preparing nanocrystalline cellulose based on tobacco waste comprises the following steps:

取100g 100目的烟草废弃物粉末,加入1000mL 5wt%的NaOH溶液,在90℃温度下提取80min然后,加入100mL 5wt%H2O2,继续回流90min,离心去除上清液,去离子水洗至中性,冷冻真空干燥,得到纤维素。Take 100g 100-mesh tobacco waste powder, add 1000mL 5wt% NaOH solution, extract at 90℃ for 80min, then add 100mL 5wt% H 2 O 2 , continue to reflux for 90min, centrifuge to remove supernatant, wash with deionized water to neutrality, freeze-dry in vacuum to obtain cellulose.

称取纤维素10g,按照料液比1:10,加入100mL硫酸-低共熔溶剂混合溶液,在95℃下催化水解5h,加入去离子水混合后离心,反复操作3-5次,然后采用截留分子量≥2000Da的透析袋透析,直至纳米晶纤维素悬浊液的pH值约为7,在8000r/min的转速下离心10min,真空冷冻干燥获得纳米晶纤维素。硫酸-低共熔溶剂耦合溶液配制方法为:乳酸与丙三醇按照质量比1:1混合,放入超声波中加热超声30min,然后35wt%硫酸与其按照比例为1:3混合,即制得硫酸-低共熔溶剂,即制得硫酸-低共熔溶剂。Weigh 10g of cellulose, add 100mL of sulfuric acid-low eutectic solvent mixed solution according to the solid-liquid ratio of 1:10, catalytically hydrolyze at 95°C for 5h, add deionized water and mix, centrifuge, repeat the operation 3-5 times, and then dialyze with a dialysis bag with a molecular weight cutoff of ≥2000Da until the pH value of the nanocrystalline cellulose suspension is about 7, centrifuge at a speed of 8000r/min for 10min, and vacuum freeze-dry to obtain nanocrystalline cellulose. The preparation method of sulfuric acid-low eutectic solvent coupling solution is: lactic acid and glycerol are mixed in a mass ratio of 1:1, placed in an ultrasonic wave for heating and ultrasonication for 30min, and then 35wt% sulfuric acid is mixed with it in a ratio of 1:3 to obtain sulfuric acid-low eutectic solvent.

本实施例的纳米晶纤维素的得率为27.3%。The yield of nanocrystalline cellulose in this example is 27.3%.

实施例7Example 7

一种基于烟草废弃物的纳米晶纤维素的制备方法,包括以下步骤:A method for preparing nanocrystalline cellulose based on tobacco waste comprises the following steps:

取100g 200目的烟草废弃物粉末,加入1000mL 5wt%的NaOH溶液,在90℃温度下提取80min然后,加入200mL 5wt%H2O2,继续回流90min,离心去除上清液,去离子水洗至中性,冷冻真空干燥,得到纤维素。Take 100g 200-mesh tobacco waste powder, add 1000mL 5wt% NaOH solution, extract at 90℃ for 80min, then add 200mL 5wt% H2O2 , continue to reflux for 90min, centrifuge to remove supernatant, wash with deionized water to neutrality, freeze-dry in vacuum to obtain cellulose.

称取纤维素10g,按照料液比1:10,加入100mL硫酸-低共熔溶剂混合溶液,在95℃下催化水解5h,加入去离子水混合后离心,反复操作3-5次,然后采用截留分子量≥2000Da的透析袋透析,直至纳米晶纤维素悬浊液的pH值约为7,在8000r/min的转速下离心10min,真空冷冻干燥获得纳米晶纤维素。硫酸-低共熔溶剂耦合溶液配制方法为:乳酸与丙三醇按照质量比1:4混合,放入超声波中加热超声30min,然后35wt%硫酸与其按照比例为1:3混合,即制得硫酸-低共熔溶剂,即制得硫酸-低共熔溶剂。Weigh 10g of cellulose, add 100mL of sulfuric acid-low eutectic solvent mixed solution according to the solid-liquid ratio of 1:10, catalytically hydrolyze at 95°C for 5h, add deionized water and mix, centrifuge, repeat the operation 3-5 times, and then dialyze with a dialysis bag with a molecular weight cutoff of ≥2000Da until the pH value of the nanocrystalline cellulose suspension is about 7, centrifuge at a speed of 8000r/min for 10min, and vacuum freeze-dry to obtain nanocrystalline cellulose. The preparation method of sulfuric acid-low eutectic solvent coupling solution is: lactic acid and glycerol are mixed in a mass ratio of 1:4, placed in an ultrasonic wave for heating and ultrasonication for 30min, and then 35wt% sulfuric acid is mixed with it in a ratio of 1:3 to obtain sulfuric acid-low eutectic solvent.

本实施例的纳米晶纤维素的得率为27.3%。The yield of nanocrystalline cellulose in this example is 27.3%.

实施例8Example 8

一种基于烟草废弃物的纳米晶纤维素的制备方法,包括以下步骤:A method for preparing nanocrystalline cellulose based on tobacco waste comprises the following steps:

取100g 150目的烟草废弃物粉末,加入1000mL 3wt%的NaOH溶液,在90℃温度下提取90min然后,加入200mL 20wt%H2O2,继续回流90min,离心去除上清液,去离子水洗至中性,冷冻真空干燥,得到纤维素。Take 100g 150 mesh tobacco waste powder, add 1000mL 3wt% NaOH solution, extract at 90℃ for 90min, then add 200mL 20wt % H2O2 , continue to reflux for 90min, centrifuge to remove supernatant, wash with deionized water to neutrality, freeze-dry in vacuum to obtain cellulose.

称取纤维素10g,按照料液比1:10,加入100mL硫酸-低共熔溶剂混合溶液,在95℃下催化水解5h,加入去离子水混合后离心,反复操作3-5次,然后采用截留分子量≥2000Da的透析袋透析,直至纳米晶纤维素悬浊液的pH值约为7,在8000r/min的转速下离心10min,真空冷冻干燥获得纳米晶纤维素。硫酸-低共熔溶剂耦合溶液配制方法为:草酸、乳酸与丙三醇按照质量比1:1:8混合,放入超声波中加热超声30min,然后35wt%硫酸与其按照比例为1:3混合,即制得硫酸-低共熔溶剂,即制得硫酸-低共熔溶剂。Weigh 10g of cellulose, add 100mL of sulfuric acid-low eutectic solvent mixed solution according to the solid-liquid ratio of 1:10, catalytically hydrolyze at 95°C for 5h, add deionized water and mix, centrifuge, repeat the operation 3-5 times, and then dialyze with a dialysis bag with a molecular weight cutoff of ≥2000Da until the pH value of the nanocrystalline cellulose suspension is about 7, centrifuge at a speed of 8000r/min for 10min, and vacuum freeze-dry to obtain nanocrystalline cellulose. The preparation method of sulfuric acid-low eutectic solvent coupling solution is: oxalic acid, lactic acid and glycerol are mixed in a mass ratio of 1:1:8, placed in an ultrasonic wave for heating and ultrasonication for 30min, and then 35wt% sulfuric acid is mixed with it in a ratio of 1:3 to obtain sulfuric acid-low eutectic solvent.

本实施例的纳米晶纤维素的得率为29.3%。The yield of nanocrystalline cellulose in this example is 29.3%.

实施例9Example 9

取100g 200目的烟草废弃物粉末,加入1500mL 1wt%的NaOH溶液,在100℃温度下提取60min然后,加入100mL 30wt%H2O2,降温至50℃继续回流30min,离心去除上清液,去离子水洗至中性,冷冻真空干燥,得到纤维素。Take 100g 200-mesh tobacco waste powder, add 1500mL 1wt% NaOH solution, extract at 100℃ for 60min, then add 100mL 30wt% H 2 O 2 , cool to 50℃ and continue to reflux for 30min, centrifuge to remove supernatant, wash with deionized water until neutral, freeze-dry in vacuum to obtain cellulose.

称取纤维素10g,按照料液比1:10,加入100mL硫酸-低共熔溶剂耦合溶液,在100℃下催化水解5h,加入去离子水混合后离心,反复操作4次,然后采用截留分子量≥2000Da的透析袋透析,直至纳米晶纤维素悬浊液的pH值约为7,在8000r/min的转速下离心10min,真空冷冻干燥获得纳米晶纤维素。硫酸-低共熔溶剂耦合溶液配制方法为:草酸、乳酸与丙三醇按照质量比1:1:4混合,放入超声波中加热超声30min,然后35wt%硫酸与其按照比例为1:3混合,即制得硫酸-低共熔溶剂,即制得硫酸-低共熔溶剂。Weigh 10g of cellulose, add 100mL of sulfuric acid-deep eutectic solvent coupling solution according to a solid-liquid ratio of 1:10, catalytically hydrolyze at 100°C for 5h, add deionized water and mix, centrifuge, repeat the operation 4 times, and then dialyze with a dialysis bag with a molecular weight cutoff of ≥2000Da until the pH value of the nanocrystalline cellulose suspension is about 7, centrifuge at a speed of 8000r/min for 10min, and vacuum freeze-dry to obtain nanocrystalline cellulose. The preparation method of sulfuric acid-deep eutectic solvent coupling solution is: oxalic acid, lactic acid and glycerol are mixed in a mass ratio of 1:1:4, placed in an ultrasonic wave for heating and ultrasonication for 30min, and then 35wt% sulfuric acid is mixed with it in a ratio of 1:3 to obtain a sulfuric acid-deep eutectic solvent.

本实施例的纳米晶纤维素的得率为29.1%。The yield of nanocrystalline cellulose in this example is 29.1%.

对比例1Comparative Example 1

取100g 150目的烟草废弃物粉末,加入2000mL 5%的NaOH溶液,在80℃温度下提取60min然后,100mL 5%H2O2,继续回流1h,离心去除上清液,去离子水洗至中性,冷冻真空干燥,得到纤维素。Take 100g 150 mesh tobacco waste powder, add 2000mL 5% NaOH solution, extract at 80℃ for 60min, then add 100mL 5% H 2 O 2 , continue to reflux for 1h, centrifuge to remove supernatant, wash with deionized water until neutral, freeze-dry in vacuum to obtain cellulose.

称取纤维素10g,按照料液比1:8,加入80mL浓度为35wt%硫酸溶液,在90℃下催化水解4h,加入去离子水混合后离心,反复操作5次,然后采用截留分子量≥2000Da的透析袋透析,直至纳米晶纤维素悬浊液的pH值约为7,在8000r/min的转速下离心10min,真空冷冻干燥获得纳米晶纤维素。Weigh 10 g of cellulose, add 80 mL of 35 wt% sulfuric acid solution at a solid-liquid ratio of 1:8, catalytic hydrolysis at 90 ° C for 4 h, add deionized water and mix, then centrifuge, repeat the operation 5 times, and then dialyze using a dialysis bag with a molecular weight cutoff ≥ 2000 Da until the pH value of the nanocrystalline cellulose suspension is about 7, centrifuge at 8000 r/min for 10 min, and vacuum freeze-dry to obtain nanocrystalline cellulose.

本对比例的纳米晶纤维素得率为12.5%。The yield of nanocrystalline cellulose in this comparative example is 12.5%.

对比例2Comparative Example 2

取100g 150目的烟草废弃物粉末,加入2000mL 5%的NaOH溶液,在80℃温度下提取60min然后,100mL 5%H2O2,继续回流1h,离心去除上清液,去离子水洗至中性,冷冻真空干燥,得到纤维素。Take 100g 150 mesh tobacco waste powder, add 2000mL 5% NaOH solution, extract at 80℃ for 60min, then add 100mL 5% H 2 O 2 , continue to reflux for 1h, centrifuge to remove supernatant, wash with deionized water until neutral, freeze-dry in vacuum to obtain cellulose.

称取纤维素10g,按照料液比1:8,加入80mL硫酸-草酸混合溶液,在90℃下催化水解4h,加入去离子水混合后离心,反复操作5次,然后采用截留分子量≥2000Da的透析袋透析,直至纳米晶纤维素悬浊液的pH值约为7,在8000r/min的转速下离心10min,真空冷冻干燥获得纳米晶纤维素。硫酸-草酸混合溶液配制方法为:草酸与纯净水按照1:4比例混合溶解,然后35wt%硫酸与其按照比例为1:3混合。Weigh 10g of cellulose, add 80mL of sulfuric acid-oxalic acid mixed solution according to the solid-liquid ratio of 1:8, catalytically hydrolyze at 90℃ for 4h, add deionized water and mix, centrifuge, repeat the operation 5 times, and then dialyze with a dialysis bag with a molecular weight cutoff of ≥2000Da until the pH value of the nanocrystalline cellulose suspension is about 7, centrifuge at a speed of 8000r/min for 10min, and vacuum freeze-dry to obtain nanocrystalline cellulose. The sulfuric acid-oxalic acid mixed solution is prepared by mixing and dissolving oxalic acid and pure water in a ratio of 1:4, and then mixing 35wt% sulfuric acid with it in a ratio of 1:3.

本对比例的纳米晶纤维素得率为17.2%。The yield of nanocrystalline cellulose in this comparative example is 17.2%.

对比例3Comparative Example 3

取100g 150目的烟草废弃物粉末,加入2000mL 5%的NaOH溶液,在80℃温度下提取60min然后,100mL 5%H2O2,继续回流1h,离心去除上清液,去离子水洗至中性,冷冻真空干燥,得到纤维素。Take 100g 150 mesh tobacco waste powder, add 2000mL 5% NaOH solution, extract at 80℃ for 60min, then add 100mL 5% H 2 O 2 , continue to reflux for 1h, centrifuge to remove supernatant, wash with deionized water until neutral, freeze-dry in vacuum to obtain cellulose.

称取纤维素10g,按照料液比1:8,加入80mL硫酸-低共熔溶剂混合溶液,在90℃下催化水解4h,加入去离子水混合后离心,反复操作5次,然后采用截留分子量≥2000Da的透析袋透析,直至纳米晶纤维素悬浊液的pH值约为7,在8000r/min的转速下离心10min,真空冷冻干燥获得纳米晶纤维素。硫酸-低共熔溶剂混合溶液配制方法为:草酸:氯化胆碱:纯净水按照4:1:4比例混合溶解,然后35wt%硫酸与其按照比例为1:3混合。Weigh 10g of cellulose, add 80mL of sulfuric acid-low eutectic solvent mixed solution according to the solid-liquid ratio of 1:8, catalytic hydrolysis at 90°C for 4h, add deionized water and mix, centrifuge, repeat the operation 5 times, and then dialyze with a dialysis bag with a molecular weight cutoff of ≥2000Da until the pH value of the nanocrystalline cellulose suspension is about 7, centrifuge at a speed of 8000r/min for 10min, and vacuum freeze-dry to obtain nanocrystalline cellulose. The sulfuric acid-low eutectic solvent mixed solution is prepared as follows: oxalic acid: choline chloride: purified water are mixed and dissolved in a ratio of 4:1:4, and then 35wt% sulfuric acid is mixed with it in a ratio of 1:3.

本对比例的纳米晶纤维素得率为20.1%。The yield of nanocrystalline cellulose in this comparative example is 20.1%.

从实施例3与对比例1-3的纳米晶纤维素得率可以看出,将硫酸与低共熔溶剂混合使用,可以显著降低硫酸用量,在较少硫酸用量的前提下提高纳米晶纤维素的得率。同时,采用硫酸-低共熔溶剂耦合溶液对纤维素纳米晶得率也要高于硫酸-草酸组。此外,本发明还与有机酸与碱性化合物所组成的低共熔溶剂进行了对比,本发明不但具有更高的得率,并且所制备纤维素纳米晶的热稳定性更好,这得益于多元醇可使纤维素充分溶胀,当多元醇和羧酸组成低共熔溶剂时,使纤维素溶胀更充分,获得的纳米晶纤维素结晶度更高,因而更稳定。It can be seen from the yield of nanocrystalline cellulose in Example 3 and Comparative Examples 1-3 that the use of sulfuric acid mixed with a low eutectic solvent can significantly reduce the amount of sulfuric acid used, thereby increasing the yield of nanocrystalline cellulose under the premise of less sulfuric acid use. At the same time, the yield of cellulose nanocrystals using a sulfuric acid-low eutectic solvent coupling solution is also higher than that of the sulfuric acid-oxalic acid group. In addition, the present invention is also compared with a low eutectic solvent composed of an organic acid and an alkaline compound. The present invention not only has a higher yield, but also has better thermal stability of the prepared cellulose nanocrystals, thanks to the fact that polyols can fully swell cellulose. When polyols and carboxylic acids form a low eutectic solvent, cellulose is more fully swollen, and the obtained nanocrystalline cellulose has a higher crystallinity and is therefore more stable.

以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1.一种基于烟草废弃物的纤维素纳米晶的制备方法,其特征在于,包括以下步骤:1. A method for preparing cellulose nanocrystals based on tobacco waste, characterized in that it comprises the following steps: (1)提取烟草废弃物中的纤维素;(1) Extracting cellulose from tobacco waste; (2)将纤维素在硫酸-低共熔溶剂耦合溶液中溶胀酸解,得到纳米晶纤维素悬浊液,将纳米晶纤维素悬浊液离心分离、透析、干燥得到纳米晶纤维素;(2) swelling and acid-hydrolyzing cellulose in a sulfuric acid-low eutectic solvent coupling solution to obtain a nanocrystalline cellulose suspension, and centrifuging, dialyzing, and drying the nanocrystalline cellulose suspension to obtain nanocrystalline cellulose; 所述硫酸-低共熔溶剂耦合溶液包括硫酸溶液和低共熔溶剂;The sulfuric acid-deep eutectic solvent coupling solution comprises a sulfuric acid solution and a deep eutectic solvent; 所述低共熔溶剂包括有机酸和多元醇;The deep eutectic solvent comprises an organic acid and a polyol; 所述有机酸和多元醇的质量比为1:(1-4);The mass ratio of the organic acid to the polyol is 1:(1-4); 所述硫酸溶液与低共熔溶剂的质量比为1:(0.25-3)。The mass ratio of the sulfuric acid solution to the low eutectic solvent is 1:(0.25-3). 2.根据权利要求1所述的基于烟草废弃物的纤维素纳米晶的制备方法,其特征在于,所述纤维素与硫酸-低共熔溶剂耦合溶液的料液比为1:(5-10)g/mL。2. The method for preparing cellulose nanocrystals based on tobacco waste according to claim 1, characterized in that the solid-liquid ratio of the cellulose to the sulfuric acid-low eutectic solvent coupling solution is 1: (5-10) g/mL. 3.根据权利要求1所述的基于烟草废弃物的纤维素纳米晶的制备方法,其特征在于,所述有机酸为草酸、乳酸或马来酸中的任意一种或两种以上;所述多元醇为丙三醇或乙二醇。3. The method for preparing cellulose nanocrystals based on tobacco waste according to claim 1, characterized in that the organic acid is any one or more of oxalic acid, lactic acid or maleic acid; and the polyol is glycerol or ethylene glycol. 4.根据权利要求1所述的基于烟草废弃物的纤维素纳米晶的制备方法,其特征在于,所述硫酸溶液的浓度为25-35wt%。4. The method for preparing cellulose nanocrystals based on tobacco waste according to claim 1, characterized in that the concentration of the sulfuric acid solution is 25-35wt%. 5.根据权利要求1所述的基于烟草废弃物的纤维素纳米晶的制备方法,其特征在于,所述溶胀酸解的温度为80-100℃,时间为3-5 h。5. The method for preparing cellulose nanocrystals based on tobacco waste according to claim 1, characterized in that the temperature of the swelling and acid hydrolysis is 80-100°C and the time is 3-5 h. 6.根据权利要求1-5任一项所述的基于烟草废弃物的纤维素纳米晶的制备方法,其特征在于,所述步骤(1)中提取烟草废弃物中的纤维素的方法为:将烟草废弃物粉末与NaOH溶液搅拌混匀,高温回流,加入H2O2溶液,经过分离、洗涤、干燥后获得纤维素。6. The method for preparing cellulose nanocrystals based on tobacco waste according to any one of claims 1 to 5, characterized in that the method for extracting cellulose from tobacco waste in step (1) is: stirring and mixing tobacco waste powder with NaOH solution, refluxing at high temperature, adding H2O2 solution, and obtaining cellulose after separation, washing and drying. 7.根据权利要求6所述的基于烟草废弃物的纤维素纳米晶的制备方法,其特征在于,烟草废弃物粉末与NaOH溶液的料液比为1:(8-20)g/mL;所述烟草废弃物粉末粒度为100-200目,NaOH溶液的浓度为1-5wt%。7. The method for preparing cellulose nanocrystals based on tobacco waste according to claim 6, characterized in that the solid-liquid ratio of tobacco waste powder to NaOH solution is 1: (8-20) g/mL; the particle size of the tobacco waste powder is 100-200 mesh, and the concentration of the NaOH solution is 1-5wt%. 8.根据权利要求7所述的基于烟草废弃物的纤维素纳米晶的制备方法,其特征在于,所述高温回流的温度为70-100℃,时间为60-90 min;高温回流后的溶液温度为50-80℃时加入浓度为3-30wt%的H2O2溶液,烟草废弃物粉末与H2O2溶液的料液为1:(0.5-2)g/mL,保持此温度30-90min。8. The method for preparing cellulose nanocrystals based on tobacco waste according to claim 7 is characterized in that the temperature of the high-temperature reflux is 70-100°C and the time is 60-90 min; when the solution temperature after high-temperature reflux is 50-80°C, a H2O2 solution with a concentration of 3-30wt % is added, the feed liquid ratio of tobacco waste powder to H2O2 solution is 1: (0.5-2) g/mL, and this temperature is maintained for 30-90 min.
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