CN113622051B - Preparation method of bamboo holocellulose nanofibers with high length-diameter ratio and high hemicellulose content - Google Patents
Preparation method of bamboo holocellulose nanofibers with high length-diameter ratio and high hemicellulose content Download PDFInfo
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Abstract
The invention discloses a preparation method of bamboo holocellulose nanofibers with high length-diameter ratio and high hemicellulose content, which comprises the steps of treating bamboo holocellulose by using acetic acid as an auxiliary eutectic solvent under the condition of microwave radiation, carrying out solid-liquid separation after treatment, dispersing solids, and preparing bamboo holocellulose nanofibers through a microjet machine after homogenization; wherein, the length-diameter ratio of the bamboo holocellulose nano-fiber is not less than 300, and the content of hemicellulose is not less than 14%. The method can effectively improve the length-diameter ratio of the nano Holocellulose (HCNF), the obtained HCNF hemicellulose content and the acetylation degree of the cellulose are higher, and the obtained bamboo nano holocellulose has the advantages of adjustable scale, uniform dispersion and the like. Meanwhile, the method has the advantages of simple process, mild reaction conditions, environmental friendliness, easiness in operation and the like, and has high application potential.
Description
Technical Field
The invention belongs to the technical field of cellulose treatment, and particularly relates to a preparation method of bamboo holocellulose nanofibers with high length-diameter ratio and high hemicellulose content.
Background
In recent years, due to environmental pollution and increasing shortage of resources, the search and research for nanostructured materials are gradually drawing attention, and biomass renewable and sustainable materials are becoming a research focus. The environment-friendly wood fiber resource not only has good renewability, but also has higher chemical or physical modification potential. Cellulose is the most abundant natural polymer on earth and is widely used as a raw material for functional applications. Cellulose, the main component of lignocellulosic biomass, consists of D-glucopyranose linked with β (1-4) glycosidic bonds. Nanocellulose with unique properties can generally be formed by a variety of methods due to its unique two-phase and aggregated structure. Nanocellulose includes Cellulose Nanocrystals (CNC), cellulose Nanofibers (CNF), and the like. Where CNF comprises crystalline and amorphous regions of the cellulose supramolecular chains, typically 3-100 nm in diameter and > 500nm in length. The CNF has strong mechanical property and can be prepared by mechanical, chemical and biological methods, the final strength is 2-6GPa, and the crystal modulus can reach 138GPa.
The following main methods for preparing nanocellulose have been reported:
CN110128555A discloses a method for obtaining cellulose nanocrystals by using pretreated biomass as a raw material and treating the raw material with an organic solvent, an ionic liquid and a cellulose solvent, but the treatment time is long, more organic solvents are used, and the maximum yield of the final cellulose nanocrystals is 71%.
Sonakshi Maitia et al [ Maiti S, jayaramudu J, das K, et al preparation and characterization of nano-cellulose with new shape from differential precursor [ J ]. Carbohydrate Polymers,2013, 98 (1): 562-567 using Chinese cotton, african cotton and waste napkin as raw materials, respectively, hydrolyzing with acid (47% sulfuric acid) under stirring to obtain nanocellulose with particle size of 30-60nm, 10-90nm and 2-10 nm, but the method uses more strong acid and is violent.
The university of santa paul, bras J, novo team [ Novo L P,
A，et al.A study of the production of cellulose nanocrystals through subcritical water hydrolysis[J].Industrial Crops and Products，2016，93：88-95.]the cellulose is hydrolyzed by utilizing the high ionization efficiency, high activity and high diffusion of subcritical water, pure water is heated and pressurized to be in a subcritical state to process MCC, and CNC with the diameter of about 55nm and the length of about 242nm is prepared, the crystallinity of the CNC is 79%, and the yield of the CNC is 21.9%.
Rostami et al [ Rostami J, mathew AP, edlund U.Zwitterionic esterified cells 1ose Nanofibrils [ J ]. Molecules,2019, 24 (17): 3147 and preparing the zwitterion acetylated CNF by acetylation, oxidation, schiff base reaction, hydroboration reduction, quaternary ammonium salt and other series reactions. Wherein acetylation is carried out in glacial acetic acid, the reaction time is short, only 90min, and monoacetylated CNF with hydroxyl is generated and can be used for further post-modification. It is thus clear that acetylation provides a good basis for multifunctional modification of CNF.
Therefore, the existing method for preparing the nano-cellulose has the problems of little diversity of chemical components of the obtained nano-fiber material, high energy consumption and long time for treatment, low hemicellulose content of the nano-fiber and the like, and can not completely meet the use requirement.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the preparation method of the bamboo holocellulose nanofiber with high length-diameter ratio and high hemicellulose content, which not only can effectively improve the length-diameter ratio of HCNF, but also has higher HCNF hemicellulose content and higher acetylation degree of cellulose, and the obtained bamboo holocellulose has the advantages of adjustable scale, uniform dispersion and the like.
A preparation method of bamboo holocellulose nanofibers with high length-diameter ratio and high hemicellulose content comprises the following steps: treating the bamboo holocellulose by adopting acetic acid as an auxiliary eutectic solvent under the condition of microwave radiation, carrying out solid-liquid separation after the treatment is finished, dispersing the solid, and homogenizing to obtain bamboo holocellulose nanofibers by a microfluidizer; wherein, the length-diameter ratio of the bamboo holocellulose nano-fiber is not lower than 300, and the content of hemicellulose is not higher than 20%.
The hydrogen bond donor of the eutectic solvent is zinc acetate, the hydrogen bond acceptor is choline chloride, and the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1: 2.
The solid-liquid mass volume ratio of the bamboo holocellulose to the eutectic solvent is 1 g: 50mL.
The molar ratio of the acetic acid to the eutectic solvent is 1: 1-3.
The microwave radiation power is 600W, the treatment temperature is 120-140 ℃, and the treatment time is 10min.
And the step of dispersing the solid is to cool the bamboo holocellulose residue after solid-liquid separation to room temperature, thoroughly wash the bamboo holocellulose residue with deionized water, freeze-dry the bamboo holocellulose residue, and then re-disperse the bamboo holocellulose residue in the deionized water.
According to the preparation method of the bamboo holocellulose nanofiber with high length-diameter ratio and high hemicellulose content, the power of a homogenizer adopted for homogenization is 650W, and the homogenization treatment time is 15min. After homogenization, the sample was rapidly centrifuged and the supernatant was passed through a microfluidizer.
According to the preparation method of the bamboo holocellulose nanofiber with high length-diameter ratio and high hemicellulose content, a sample is homogenized and then subjected to rapid centrifugation, and supernatant is passed through a micro-jet machine; the operating pressure of the microfluidizer used was 600bar, and the operation was carried out more than 3 times.
The preparation method of the bamboo holocellulose nanofiber with high length-diameter ratio and high hemicellulose content comprises the following specific steps:
(1) Preparing a eutectic solvent; wherein, the hydrogen bond donor is zinc acetate, the hydrogen bond acceptor is choline chloride, and the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1: 2;
(2) Taking bamboo holocellulose powder and a eutectic solvent into a microwave reactor, wherein the solid-liquid ratio of the bamboo holocellulose powder to DES is 1 g: 50mL, and adding acetic acid, wherein the molar ratio of the acetic acid to the eutectic solvent is 1: 1-3; uniformly mixing, and then treating for 10 minutes at the temperature of 120-140 ℃ under the microwave irradiation power of 600W;
(3) Cooling to room temperature after treatment, performing solid-liquid separation, thoroughly washing the solid with deionized water, and freeze-drying the powder residue after washing; and dispersed in deionized water;
(4) Carrying out mechanical homogenization and preparing bamboo holocellulose nanofibers by a microfluid machine; wherein the power of a homogenizer adopted for homogenization is 650W, and the homogenization treatment time is 15min; the operating pressure of the microfluidizer used was 600bar, and the operation was carried out more than 3 times.
The application is inspired by the action relation of cellulose and hemicellulose matrixes in higher plants, and the improvement of the mechanical strength of the plants due to the interaction of polysaccharides is applied to the field of nanofiber preparation. Under the microwave irradiation, the bamboo wood holocellulose nanofiber (HCNF) rich in hemicellulose is rapidly produced through the treatment of dilute acetic acid-assisted zinc acetate (ZnAc)/choline chloride (ChCl) eutectic solvent (DES). The chemical composition diversity of the nanofiber material is improved to a certain extent in a controllable manner, and the problems of high energy consumption, long time and low hemicellulose content of the nanofiber are solved.
Has the advantages that: compared with the prior art, the invention has the advantages that:
1) The method can effectively improve the length-diameter ratio of the HCNF, the content of the HCNF hemicellulose and the acetylation degree of the cellulose are higher, and the obtained bamboo wood nano holocellulose has the advantages of adjustable scale, uniform dispersion and the like.
2) The method has the advantages of simple flow, mild reaction conditions, environmental friendliness, easiness in operation and the like, has the characteristics of short time and high efficiency, and has practicability for raw preparation of the bamboo holocellulose nanofibers by pretreating bamboo raw materials.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) image of nano holocellulose after pretreatment with a eutectic solvent;
FIG. 2 is a diagram showing a distribution of the particle size of nano-hedral cellulose after pretreatment with a eutectic solvent;
FIG. 3 is a comparison graph of the mechanical strength of the nano holocellulose film prepared by the method and the mechanical strength of the nano holocellulose film prepared by the traditional Tempo oxidation method.
Detailed Description
In order that the invention may be more readily understood, reference will now be made in detail to the following examples of the invention, which are intended to be illustrative only and not limiting.
The raw material bamboo holocellulose adopted in the following examples can be a product directly sold in the market or can be self-made, and the typical method comprises the following steps: bleaching bamboo with sodium chlorite/acetic acid to prepare the bamboo holocellulose. The bamboo holocellulose mainly comprises the following components: cellulose (53.4%), hemicellulose (22.8%) and a small amount of lignin (9.6%).
Example 1
The preparation method of the bamboo holocellulose nano-fiber with high length-diameter ratio and high hemicellulose content comprises the following steps:
(1) Preparing a eutectic solvent (DES): taking Zinc Acetate (ZA) as a hydrogen bond donor, taking choline chloride (ChCl) as a hydrogen bond acceptor, uniformly mixing the zinc acetate and the choline chloride at a molar ratio of the donor to the acceptor of 1: 2, and heating the mixture at 80 ℃ for 4h by magnetic stirring until a uniform transparent liquid appears.
(2) Pretreatment: 0.5g of bamboo holocellulose powder and 25mL of zinc acetate/choline chloride (ZAC) were added to the Teflon container of the microwave reactor. The solid-liquid ratio of the bamboo holocellulose powder to DES is 1:50 (g/mL) and acetic acid is added in a molar ratio of acetic acid to DES of 1: 1 (ZAC 1-1), or 1: 2 (ZAC 2-1), or 1:3 (ZAC 3-1). The mixture was stirred and mixed well using a glass rod. The mixture was treated at 120 ℃ and a microwave irradiation power of 600W for 10 minutes. After pretreatment, the mixture was cooled to room temperature, rinsed thoroughly with deionized water and the powder residue was freeze dried after washing.
(3) Preparation of HCNF: taking the pretreated bamboo holocellulose, re-dispersing the bamboo holocellulose in deionized water at a concentration of 5% (w/v), and homogenizing the sample for 15min by using a homogenizer. Then, the mixture was centrifuged rapidly, and the supernatant was passed through a microfluidizer at an operating pressure of 600bar for 5 times to obtain HCNF.
Example 2
The preparation method of the bamboo holocellulose nano-fiber with high length-diameter ratio and high hemicellulose content comprises the following steps:
(1) Preparing a eutectic solvent (DES): zinc Acetate (ZA) was used as a hydrogen bond donor and choline chloride (ChCl) as a hydrogen bond acceptor, and the donor and acceptor were uniformly mixed at a molar ratio of 1: 2, and the mixture was heated at 80 ℃ for 4 hours with magnetic stirring until a uniform transparent liquid appeared.
(2) Pretreatment: 0.5g of bamboo holocellulose powder and 25mL of zinc acetate/choline chloride (ZAC) were added to the Teflon container of the microwave reactor. The solid-liquid ratio of the bamboo holocellulose powder to DES is 1:50 (g/mL), and acetic acid is added, wherein the molar ratio of the acetic acid to DES is 1: 1 (ZAC 1-2), or 1: 2 (ZAC 2-2), or 1:3 (ZAC 3-2). The mixture was stirred and mixed well using a glass rod. The mixture was treated at 140 ℃ and a microwave irradiation power of 600W for 10 minutes. After pretreatment, the mixture was cooled to room temperature, rinsed thoroughly with deionized water and the powder residue was freeze dried after washing.
(3) Preparation of HCNF: taking the pretreated bamboo holocellulose, re-dispersing the bamboo holocellulose in deionized water at a concentration of 5% (w/v), and homogenizing the sample for 15min by using a homogenizer. Then, the supernatant was subjected to rapid centrifugation, and the HCNF was obtained by passing the supernatant through a microfluidizer at an operating pressure of 600bar for 5 times.
Example 3
The 6 HCNF products prepared in examples 1 and 2 and designated ZAC1-1, ZAC2-1, (ZAC 3-1, ZAC1-2, ZAC2-2, ZAC3-2, respectively, were characterized and the results are shown in table 1.
1) The recovery rate is calculated as: recovery = mass of HCNF (g)/mass of bamboo holocellulose powder (g) × 100%.
2) And (3) AFM observation: diluting the nano holocellulose suspension by 0.5 percent, dripping the nano holocellulose suspension on a smooth mica sheet, and observing the morphology of the nano fibers by using an atomic force microscope after the nano holocellulose suspension is naturally dried to obtain the average length (nm), the average width (nm) and the length-diameter ratio.
3) Determination of crystallinity: the apparatus used was an X-ray diffractometer and the crystallinity (%) = crystalline region peak area/(crystalline region peak area + amorphous region peak area) × 100%.
4) And (3) measuring the content of glucan and xylan: after sulfuric acid hydrolysis, the content of components in the hydrolysate is determined by ion chromatography by adopting a method for determining the components of the wood fiber specially used for the American energy laboratory; wherein,
glucose content (%) = glucose content in hydrolysate (g)/mass of original enzymolysis material (g) × 100%;
the xylan content (%) = the xylose content (g) in the hydrolysate/the original enzymolysis material mass (g) × 100%;
5) Measurement of acetylation: the freeze-dried sample was subjected to peak fitting by X-ray photoelectron spectroscopy, and the acetylation degree =288.5eV peak area/(284.7 eV peak area +286eV peak area).
TABLE 1 recovery of nano holocellulose and analysis of the composition data
Fig. 1 is a Transmission Electron Microscope (TEM) image of nano-hedral cellulose after pretreatment with a eutectic solvent;
FIG. 2 is a diagram showing a distribution of the particle size of nano-hedral cellulose after pretreatment with a eutectic solvent; from the results of fig. 1, fig. 2 and table 1, it can be known that the nano holocellulose has typical fiber morphology, uniform dispersion, high length-diameter ratio and controllable scale; the nano holocellulose prepared by the embodiments has reasonable size distribution, and the content of the HCNF hemicellulose and the acetylation degree of the cellulose are both high.
Example 4
Preparing a film: HCNF prepared in the embodiments 1 and 2 is prepared into nano holocellulose suspension liquid with the mass fraction of 1%, the traditional Tempo oxidized cellulose nano fiber with the mass fraction of 1% is used as a contrast, a film is prepared by a vacuum filtration method, and a universal tensile machine is used for testing the tensile strength.
The result is shown in fig. 3, and it can be known that the prepared nano holocellulose film has more remarkable flexibility and tensile strength and higher application potential compared with the Tempo oxidized nano cellulose film.
It should be noted that the embodiment of the present invention is not limited by the above-mentioned examples, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and included in the scope of the present invention.
Claims (1)
1. A preparation method of bamboo holocellulose nanofibers with high length-diameter ratio and high hemicellulose content is characterized by comprising the following steps: treating bamboo holocellulose by adopting acetic acid as an auxiliary eutectic solvent under the condition of microwave radiation, performing solid-liquid separation after the treatment is finished, dispersing solids, and homogenizing to obtain bamboo holocellulose nanofibers through a microfluidizer; wherein, the length-diameter ratio of the bamboo holocellulose nano-fiber is not lower than 300, and the content of hemicellulose is not lower than 14 percent; the method comprises the following specific steps:
(1) Preparing a eutectic solvent; wherein, the hydrogen bond donor is zinc acetate, the hydrogen bond acceptor is choline chloride, and the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1: 2;
(2) Taking bamboo holocellulose powder and a eutectic solvent into a microwave reactor, wherein the solid-to-liquid ratio of the bamboo holocellulose powder to DES is 1 g: 50mL, and adding acetic acid, wherein the molar ratio of the acetic acid to the eutectic solvent is 1: 1-3; after being uniformly mixed, the mixture is treated for 10 minutes at the temperature of 120-140 ℃ under the microwave irradiation power of 600W;
(3) Cooling to room temperature after treatment, performing solid-liquid separation, thoroughly washing the solid with deionized water, and freeze-drying the powder residue after washing; and dispersed in deionized water;
(4) Carrying out mechanical homogenization and preparing bamboo holocellulose nanofibers by a microfluid machine; wherein, the power of a homogenizer for homogenization is 650W, and the homogenization treatment time is 15min; the operating pressure of the microfluidizer used was 600bar, and the operation was carried out more than 3 times.
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