CN113880958A - Method for preparing kelp residue nanocrystalline cellulose by using eutectic solvent and ultrasound - Google Patents
Method for preparing kelp residue nanocrystalline cellulose by using eutectic solvent and ultrasound Download PDFInfo
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Abstract
The invention discloses a method for preparing nano-crystalline cellulose from kelp residue by using a eutectic solvent and ultrasound, which belongs to the technical field of deep processing of plants, and the method can be used for extracting and preparing the nano-crystalline cellulose from the kelp residue, so that the kelp residue is changed into valuable, the environmental pollution is reduced, and the production cost of the nano-crystalline cellulose can be reduced; the method comprises the following steps: (1) mixing imidazole and glycerol to obtain a first eutectic solvent; (1) adding the kelp residue into the first eutectic solvent for soaking, filtering, washing and freeze-drying to obtain kelp treatment residue; (2) mixing choline chloride and oxalic acid dihydrate to obtain a second eutectic solvent; (3) adding the kelp treatment residues and the second eutectic solvent into a high-pressure reaction kettle for reaction, and diluting to obtain kelp residue reaction liquid; (4) centrifuging the reaction solution of the kelp residue, removing supernatant and precipitating to obtain kelp precipitate; (5) dialyzing the kelp sediment to obtain kelp suspension; (6) ultrasonic processing the kelp suspension, and freeze drying.
Description
Technical Field
The invention relates to the technical field of plant deep processing, in particular to a method for preparing kelp residue nanocrystalline cellulose by using a eutectic solvent and ultrasound.
Background
Because the kelp yield is high and the algin content is rich, the kelp seaweed extract can be industrially used for extracting and separating the algin in the kelp seaweed to prepare an important chemical product sodium alginate. During the production process of sodium alginate, a large amount of solid impurities such as kelp residue which is the residue of gel extraction is generated. The kelp residue is used as a main solid emission in the sodium alginate industry, a good utilization mode is not found at present, and a landfill disposal mode not only occupies a large area of land, but also wastes a large amount of resources.
Nanocrystalline cellulose is a rod-like nanoscale (typically under one micron in length and from a few nanometers to tens of nanometers in width) cellulose material with high strength. Nanocrystalline cellulose has several unique properties, such as being lightweight, biodegradable, high strength, high specific surface area, and the like. The conventional method for preparing nanocrystalline cellulose is to hydrolyze the cellulose with mineral acids (sulfuric acid, hydrochloric acid, phosphoric acid or mixtures thereof). Although the method is simple, the problems of serious equipment corrosion, generation of a large amount of waste acid, environmental pollution and the like exist.
The eutectic solvent is a mixture consisting of two components, namely a hydrogen bond donor and a hydrogen bond acceptor, and the components can be expanded into three or more. Because of strong hydrogen bond interaction between the hydrogen bond donor and the hydrogen bond acceptor, the melting point of the eutectic solvent is far lower than that of pure substances of each component. The eutectic solvent has the characteristics of simple preparation, low cost, low toxicity, high biodegradability and the like. The application of the eutectic solvent in many fields attracts people's attention, and particularly, the existence of intermolecular hydrogen bonds in the eutectic solvent makes it possible to destroy the hydrogen bonds of the biomass, so that the eutectic solvent has good biomass dissolving and converting capacity.
The content of cellulose in the kelp residue is about 30%, and the kelp residue is used as the raw material to prepare the nanocrystalline cellulose, so that the raw material is cheap, the waste can be utilized, the waste is changed into valuable, and the environmental pollution is reduced. Therefore, it is highly desirable to invent a method capable of effectively extracting cellulose from kelp residue by using a eutectic solvent, thereby improving the utilization rate of kelp residue.
Disclosure of Invention
The invention aims to provide a method for preparing nano-crystalline cellulose in kelp residue by using a eutectic solvent and ultrasound, which can extract and prepare the nano-crystalline cellulose in the kelp residue, change the kelp residue into valuable, reduce environmental pollution and reduce the production cost of the nano-crystalline cellulose.
The technical scheme of the invention is as follows:
a method for preparing kelp residue nanocrystalline cellulose by using a eutectic solvent and ultrasound comprises the following preparation steps:
(1) taking imidazole and glycerol according to a molar ratio of 7: 3, mixing to obtain a first eutectic solvent;
(2) adding the kelp residue into the first eutectic solvent obtained in the step (1) for soaking, filtering, washing and freeze-drying to obtain kelp treatment residue, and freezing and storing for later use;
(3) mixing choline chloride and oxalic acid dihydrate to obtain a second eutectic solvent;
(4) adding the kelp treatment residues and the second eutectic solvent obtained in the step (2) into a high-pressure reaction kettle for reaction treatment, and diluting to obtain a kelp residue reaction solution;
(5) centrifuging the reaction liquid of the kelp residue obtained in the step (4), removing supernatant and precipitating to obtain kelp precipitate;
(6) putting the kelp sediment obtained in the step (5) into a dialysis bag for dialysis treatment to obtain kelp suspension;
(7) and (4) carrying out ultrasonic treatment on the kelp suspension obtained in the step (6), and carrying out freeze drying to obtain the kelp suspension.
Further, in the step (2), the solid-to-liquid ratio of the added kelp residue to the first eutectic solvent is 1: 20w/w, the soaking temperature is 90 ℃, the soaking time is 24h, stirring treatment is carried out during soaking, and the obtained kelp processing residue is stored at the temperature below 20 ℃ below zero.
Further, in the step (3), the molar ratio of choline chloride to oxalic acid dihydrate is 1: 1 at 80 ℃ and mixing homogeneously.
Further, in the step (4), the solid-to-liquid ratio of the second eutectic solvent of the kelp treatment slag added into the high-pressure reaction kettle is 1: 40w/w, the reaction treatment time is 2.5h, the temperature is 110 ℃, the stirring speed is 220rpm, and 20 times of the initial volume of deionized water is added for dilution after the reaction is finished.
Further, in the step (5), the reaction solution of the kelp residue is centrifuged at 8000rpm for 10min, and is centrifuged and purified by deionized water during precipitation until the pH value of the supernatant is 5.
Further, in the step (6), new deionized water is added for a plurality of times during the dialysis treatment until the pH value is unchanged.
Further, in the step (7), the kelp suspension is subjected to ultrasonic treatment for 20min, and the crushing power of the ultrasonic crusher is 650W.
Further, before the step (1), the following steps are also included:
(0.1) soaking dried herba Zosterae Marinae in formalin, washing, air drying, pulverizing, sieving, adding Na2CO3Stirring and digesting the water solution, washing, collecting filter residues and drying to obtain non-decalcified kelp residues;
and (0.2) adding the non-decalcified kelp residues obtained in the step (0.1) into an EDTA aqueous solution, stirring, washing and collecting filter residues to obtain kelp residues, and freezing and storing for later use.
Further, in the step (0.1), the feed-liquid ratio of the added dried kelp to the aqueous formaldehyde solution is 1: 10, the concentration of the formaldehyde aqueous solution is 3.2 wt%, the soaking time is 24h, after being crushed, the kelp powder and the added Na are sieved by a 50-mesh sieve2CO3The feed-liquid ratio of the aqueous solution is 1: 10w/w, Na2CO3The aqueous solution had a concentration of 3 wt% and was digested for 3h with stirring at 50 ℃.
Further, in the step (0.2), the solid-to-liquid ratio of the added non-decalcified kelp residues to the EDTA aqueous solution is 1: 10w/w, the molar concentration of the EDTA aqueous solution is 0.3mol/L, the stirring time is 2 hours, and the obtained kelp residue is stored at the temperature of below 20 ℃ below zero.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to a method for preparing kelp residue nanocrystalline cellulose by using a eutectic solvent and ultrasound, which comprises the steps of adding kelp residue into a first eutectic solvent for soaking, filtering, washing, freeze-drying to obtain kelp treatment residue, and freezing and storing for later use; carrying out centrifugal treatment on the kelp treatment residues, choline chloride and oxalic acid dihydrate, removing supernate and precipitating to obtain kelp precipitates; putting into a dialysis bag for dialysis treatment to obtain a kelp suspension; performing ultrasonic treatment, and freeze-drying. The kelp residue is subjected to ultrasonic treatment sequentially by using the eutectic solvent, so that the nanocrystalline cellulose can be extracted and prepared from the kelp residue, the kelp residue is changed into valuable, the environmental pollution is reduced, and the production cost of the nanocrystalline cellulose can be reduced.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention. In the drawings:
FIG. 1 is an analysis graph of the treatment temperature of a eutectic solvent and the yield of nano-crystalline cellulose of kelp residue;
FIG. 2 is an analysis graph of the treatment time of the eutectic solvent and the yield of the nano-crystalline cellulose of the kelp residue;
FIG. 3 is an analysis chart of ultrasonic treatment conditions and yield of nano-crystalline cellulose in kelp residue;
FIG. 4 is an analysis chart of the ultrasonic treatment time and yield of nano-crystalline cellulose in kelp residue;
FIG. 5 is a FTIR spectrum of an experimental sample;
FIG. 6 is an XRD pattern of the experimental sample;
FIG. 7 is a particle size distribution diagram of an experimental sample;
fig. 8 is a projection electron micrograph of the experimental sample.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to the following embodiments, but the present invention is not limited thereto.
A method for preparing kelp residue nanocrystalline cellulose by using a eutectic solvent and ultrasound comprises the following preparation steps:
(1) taking imidazole and glycerol according to a molar ratio of 7: 3, mixing to obtain a transparent and uniform first eutectic solvent, wherein the temperature is 80 ℃ during mixing.
(2) Soaking the kelp residue in the first eutectic solvent, filtering, washing, freeze-drying to obtain kelp residue, and freezing for storage.
Wherein the solid-to-liquid ratio of the added kelp residue to the first eutectic solvent is 1: 20w/w, the soaking temperature is 90 ℃, the soaking time is 24h, the C-MAGHS-7 constant-temperature magnetic stirrer produced by Germany IKA company is used for stirring treatment during soaking, filtration and separation are carried out after soaking is finished, filter residue is fully washed by deionized water, an ALPHA1-2 LD plus vacuum freeze dryer produced by Germany Christ company is used for freeze drying to obtain kelp treatment residue, and the obtained kelp treatment residue is stored at the temperature below-20 ℃.
(3) And mixing choline chloride and oxalic acid dihydrate to obtain a second eutectic solvent. Wherein, the mol ratio of the choline chloride to the oxalic acid dihydrate is 1: 1 at 80 ℃ to obtain a transparent and uniform second eutectic solvent.
(4) And (4) adding the kelp treatment residues and the second eutectic solvent obtained in the step (3) into a high-pressure reaction kettle for reaction treatment, and diluting to obtain a kelp residue reaction liquid.
Wherein the solid-to-liquid ratio of the second eutectic solvent of the kelp treatment slag added into the high-pressure reaction kettle is 1: 40w/w, the reaction treatment time is 2.5h, the temperature of the whole system is 110 ℃, the stirring speed is 220rpm, and 20 times of the initial volume of deionized water is added for dilution after the reaction is finished. The autoclave used was a Parr 4500 autoclave manufactured by Parr Instrument corporation, USA.
(5) And (4) carrying out centrifugal treatment on the kelp residue reaction liquid obtained in the step (4), and removing supernatant liquid to precipitate so as to obtain kelp precipitate.
Wherein, the kelp residue reaction solution is centrifuged at 8000rpm for 10min, deionized water is used for centrifugation and purification during precipitation until the pH value of supernatant is 5, and precipitate is collected in a dialysis bag, wherein the dialysis bag is a dialysis bag which is produced by Viskase company of America and has the model of 8000-14000 Da.
(6) And (5) putting the kelp sediment obtained in the step (5) into a dialysis bag for dialysis treatment to obtain kelp suspension. During the dialysis treatment, new deionized water is added for a plurality of times until the pH value of the dialysate is not changed.
(7) And (4) carrying out ultrasonic treatment on the kelp suspension obtained in the step (6), and carrying out freeze drying to obtain the kelp suspension.
Wherein, the ultrasonic treatment time of the kelp suspension is 20min, the crushing power of the ultrasonic crusher is 650W, the operation time is 6s, the pause time is 3s, and the concentration is 4 wt%. Finally, freeze-drying with vacuum freeze-drying machine of ALPHA1-2 LD plus produced by Christ, Germany.
Before the step (1), the method also comprises a step of preparing the kelp residue, and specifically comprises the following steps:
(0.1) soaking dried herba Zosterae Marinae in formalin, washing, air drying, pulverizing, sieving, adding Na2CO3Stirring and digesting the water solution, washing, collecting filter residues and drying to obtain the non-decalcified kelp residues.
Wherein the feed-liquid ratio of the added dry kelp to the formaldehyde aqueous solution is 1: 10, the concentration of the formaldehyde aqueous solution is 3.2 wt%, the soaking time is 24h, after being crushed, the kelp powder and the added Na are sieved by a 50-mesh sieve2CO3The feed-liquid ratio of the aqueous solution is 1: 10w/w, Na2CO3The aqueous solution was 3 wt% and digested for 3 hours with a constant temperature magnetic stirrer C-MAGHS-7 from IKA, Germany, at a temperature of 50 ℃. After digestion, the filter residue is washed by deionized water, and the filter residue is freeze-dried by using an ALPHA1-2 LD plus vacuum freeze-drying machine produced by Christ, Germany.
And (0.2) adding the non-decalcified kelp residues obtained in the step (0.1) into an EDTA aqueous solution, stirring, washing and collecting filter residues to obtain kelp residues, and freezing and storing for later use.
Wherein the solid-to-liquid ratio of the added non-decalcified kelp residues to the EDTA aqueous solution is 1: 10w/w, the molar concentration of the EDTA aqueous solution is 0.3mol/L, stirring is carried out by using a C-MAGHS-7 constant temperature magnetic stirrer produced by the German IKA company, the stirring time is 2 hours, and the obtained kelp residue is stored at the temperature of below 20 ℃ below zero.
According to the method for preparing the nano-crystalline cellulose from the kelp residue by using the eutectic solvent and the ultrasound, the kelp residue is subjected to ultrasonic treatment sequentially by using the eutectic solvent, so that the nano-crystalline cellulose can be extracted and prepared from the kelp residue. The content of cellulose in the kelp residue is about 30 percent, and the kelp residue is taken as a nano cellulose source, so that the raw materials are cheap, the deep processing of agricultural products and the treatment of wastes are facilitated, the kelp residue is changed into valuable, the environmental pollution is reduced, the production cost of nanocrystalline cellulose can be reduced, and a new way for the comprehensive utilization of the kelp residue is opened up.
Comparative experiment
According to the method for preparing the kelp residue nanocrystalline cellulose by using the eutectic solvent and the ultrasound, the kelp residue nanocrystalline cellulose is prepared, wherein the kelp residue nanocrystalline cellulose yield is obtained by independently changing the three factors respectively through independently testing the four factors of the treatment condition of the eutectic solvent, the treatment time of the eutectic solvent, the ultrasonic treatment condition and the ultrasonic treatment time in the preparation method.
1. Experiment of change of treatment conditions of eutectic solvent
Taking 12g of kelp residue, dividing six equally into 6 groups, and preparing the kelp residue nanocrystalline cellulose by utilizing the eutectic solvent and the ultrasonic preparation method of the kelp residue nanocrystalline cellulose for each group.
And (3) adding the kelp treatment residues of 6 groups and the second eutectic solvent obtained in the step (2) into a high-pressure reaction kettle for reaction treatment respectively, and diluting to obtain a kelp residue reaction solution. Adding 6 groups of kelp processing residues into a high-pressure reaction kettle, sequentially controlling the temperature of the whole system to be 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃ and 125 ℃, and the other parameters to be the same as the preparation method of the invention, respectively preparing 6 parts of kelp residue nanocrystalline cellulose, weighing the weight of each part of kelp residue nanocrystalline cellulose, and calculating the yield of each part of kelp residue nanocrystalline cellulose to obtain an analysis chart of the processing temperature of the eutectic solvent and the yield of the kelp residue nanocrystalline cellulose, wherein the analysis chart is shown in figure 1.
2. Experiment of change in treatment time of eutectic solvent
Taking 12g of kelp residue, dividing six equally into 6 groups, and preparing the kelp residue nanocrystalline cellulose by utilizing the eutectic solvent and the ultrasonic preparation method of the kelp residue nanocrystalline cellulose for each group.
And (3) adding the kelp treatment residues of 6 groups and the second eutectic solvent obtained in the step (2) into a high-pressure reaction kettle for reaction treatment respectively, and diluting to obtain a kelp residue reaction solution. Adding 6 groups of kelp processing residues into a high-pressure reaction kettle, wherein the reaction processing time is 1.5h, 2.0h, 2.5h, 3.0h, 3.5h and 4.0h in sequence, and other parameters are the same as those of the preparation method of the invention, respectively preparing 6 parts of kelp residue nanocrystalline cellulose, weighing the weight of each part of kelp residue nanocrystalline cellulose, and calculating the yield of each part of kelp residue nanocrystalline cellulose to obtain the processing time of the eutectic solvent and an analysis chart of the yield of the kelp residue nanocrystalline cellulose, as shown in figure 2.
3. Experiment of variation of ultrasonic treatment conditions
10g of kelp residue is divided into 5 groups, and each group is respectively used for preparing the kelp residue nanocrystalline cellulose by utilizing the eutectic solvent and the method for preparing the kelp residue nanocrystalline cellulose by ultrasound.
Wherein, in the step (6), the kelp suspension liquid obtained in the 5 groups of the step (5) is respectively subjected to ultrasonic treatment and freeze drying to obtain the kelp seaweed suspension liquid. Wherein, when 5 groups of kelp suspensions are subjected to ultrasonic treatment, the crushing power of the ultrasonic crusher is 450W, 550W, 650W, 750W and 850W in sequence, other parameters are the same as the preparation method of the invention, 5 parts of kelp residue nanocrystalline cellulose are respectively prepared, the weight of each part of kelp residue nanocrystalline cellulose is weighed, and the yield of each part of kelp residue nanocrystalline cellulose is calculated to obtain an analysis chart of ultrasonic treatment conditions and the yield of kelp residue nanocrystalline cellulose, as shown in fig. 3.
4. Experiment of ultrasonic treatment time variation
Taking 8g of kelp residue, dividing into 4 groups in six equal parts, and preparing the kelp residue nanocrystalline cellulose by utilizing the eutectic solvent and the method for preparing the kelp residue nanocrystalline cellulose by ultrasound in each group.
Wherein, in the step (6), the kelp suspension liquid obtained in the 4 groups of the step (5) is respectively subjected to ultrasonic treatment and freeze drying to obtain the kelp seaweed suspension liquid. Wherein, the time for ultrasonic treatment of the 4 groups of kelp suspensions is 10min, 20min, 30min and 40min in sequence, other parameters are the same as the preparation method of the invention, 5 parts of kelp residue nanocrystalline cellulose are respectively prepared, the weight of each part of kelp residue nanocrystalline cellulose is weighed, and the yield of each part of kelp residue nanocrystalline cellulose is calculated to obtain an analysis chart of the ultrasonic treatment time and the yield of the kelp residue nanocrystalline cellulose, as shown in fig. 4.
According to the method for preparing the kelp residue nanocrystalline cellulose by using the eutectic solvent and the ultrasound, disclosed by the invention, when the kelp treatment residue and the second eutectic solvent are added into a high-pressure reaction kettle for reaction treatment, the temperature of the whole system is 110 ℃, the reaction treatment time is 2.5 hours, when the kelp suspension is subjected to the ultrasound treatment, the crushing power of an ultrasonic crusher is 650W, and the treatment time is 20min, the yield of the kelp residue nanocrystalline cellulose is highest, the final yield is 75.8%, and the preparation effect of the preparation parameter is optimal.
Examples of the experiments
Taking the kelp residue nanocrystalline cellulose prepared by the method for preparing the kelp residue nanocrystalline cellulose by using the eutectic solvent and the ultrasound as an experimental sample, and carrying out FTIR spectrum analysis on the sample to obtain an FTIR spectrogram of the experimental sample, wherein the FTIR spectrogram is shown in figure 5.
According to the figure 5, the nano-crystalline cellulose of the kelp residue prepared by the method is 1732cm-1A new absorption peak appears, which is a product after the ester group is superposed with the C ═ O vibration in the carboxyl group, and indicates that the cellulose hydroxyl group reacts with the carboxyl group in the oxalic acid to form a new ester group functional group. A series of infrared characteristic absorption peaks of cellulose can be observed from the infrared spectrogram of the experimental sample, and are at 3600-3400cm-1The wide and high strong absorption peak belongs to the O-H stretching vibration peak; 2920cm-1Is C-H stretching vibration peak; 1645cm-1Is positioned at the H-O-H bending vibration peak of the cellulose absorbed water; 1425cm-1Is C6 CH2The bending vibration peak of (1); 1163cm-1Is a C-O-C stretching vibration peak; 896cm-1Is the plane rocking vibration peak of C-H.
Taking an experimental sample, and carrying out XRD (X-ray diffraction) pattern analysis on the experimental sample to obtain an XRD pattern of the experimental sample, wherein the XRD pattern is shown in figure 6. As can be seen from fig. 6, the produced kelp residue nanocrystaline cellulose according to the present invention has characteristic peaks of typical cellulose I at 2 θ ═ 14.7 °, 16.4 °, 22.7 ° and 34.6 °, and these characteristic peaks are associated with the (110), (110), (200) and (004) crystal planes of cellulose I, respectively. The crystallinity of the kelp residue nanocrystalline cellulose is calculated to be 69.7 percent according to an empirical equation.
The particle size distribution of the experimental sample was obtained by using a Nano ZS90 type Nano-zeta potentiostat, Malvern, uk, to obtain a particle size distribution chart of the experimental sample, as shown in fig. 7. As can be seen from FIG. 7, the particle size distribution range of the nano-crystalline cellulose of kelp residue prepared by the method of the present invention is 200-1000nm, and the Zeta potential is measured to be-45.5 mV.
The experimental sample was taken and observed in a transmission electron microscope to obtain a transmission electron microscope image of the experimental sample, as shown in fig. 8. As can be seen from FIG. 8, the nano-crystalline cellulose of kelp residue prepared by the method of the present invention has a length of 200-1600nm, a diameter of 20-65nm and a length-diameter ratio of 5-800.
From the above experiments, the properties of the kelp residue nanocrystalline cellulose prepared by the method for preparing the kelp residue nanocrystalline cellulose by using the eutectic solvent and the ultrasound provided by the invention meet the use requirements.
The above description is only exemplary of the invention, and any modification, equivalent replacement, and improvement made within the spirit and scope of the present invention should be considered within the scope of the present invention.
Claims (10)
1. A method for preparing kelp residue nanocrystalline cellulose by using a eutectic solvent and ultrasound is characterized by comprising the following preparation steps:
(1) taking imidazole and glycerol according to a molar ratio of 7: 3, mixing to obtain a first eutectic solvent;
(2) adding the kelp residue into the first eutectic solvent obtained in the step (1) for soaking, filtering, washing and freeze-drying to obtain kelp treatment residue, and freezing and storing for later use;
(3) mixing choline chloride and oxalic acid dihydrate to obtain a second eutectic solvent;
(4) adding the kelp treatment residues and the second eutectic solvent obtained in the step (2) into a high-pressure reaction kettle for reaction treatment, and diluting to obtain a kelp residue reaction solution;
(5) centrifuging the reaction liquid of the kelp residue obtained in the step (4), removing supernatant and precipitating to obtain kelp precipitate;
(6) putting the kelp sediment obtained in the step (5) into a dialysis bag for dialysis treatment to obtain kelp suspension;
(7) and (4) carrying out ultrasonic treatment on the kelp suspension obtained in the step (6), and carrying out freeze drying to obtain the kelp suspension.
2. The method for preparing the kelp residue nanocrystalline cellulose by using the eutectic solvent and the ultrasound according to claim 1, wherein in the step (2), the solid-to-liquid ratio of the added kelp residue to the first eutectic solvent is 1: 20w/w, the soaking temperature is 90 ℃, the soaking time is 24h, stirring treatment is carried out during soaking, and the obtained kelp processing residue is stored at the temperature below 20 ℃ below zero.
3. The method for preparing the kelp residue nanocrystalline cellulose using the eutectic solvent and the ultrasound as claimed in claim 1, wherein, in the step (3), the molar ratio of choline chloride and oxalic acid dihydrate is 1: 1 at 80 ℃ and mixing homogeneously.
4. The method for preparing the nano-crystalline cellulose in the kelp residue by using the eutectic solvent and the ultrasound according to claim 1, wherein in the step (4), the solid-to-liquid ratio of the second eutectic solvent of the kelp residue added into the high-pressure reaction kettle is 1: 40w/w, the reaction treatment time is 2.5h, the temperature is 110 ℃, the stirring speed is 220rpm, and 20 times of the initial volume of deionized water is added for dilution after the reaction is finished.
5. The method for preparing the nano-crystalline cellulose in the kelp residue by using the eutectic solvent and the ultrasound as claimed in claim 1, wherein in the step (5), the reaction solution of the kelp residue is centrifuged at 8000rpm for 10min, and the reaction solution is centrifuged and purified by deionized water during precipitation until the pH value of the supernatant is 5.
6. The method for preparing the kelp residue nanocrystalline cellulose by using the eutectic solvent and the ultrasound according to claim 1, wherein in the step (6), new deionized water is added many times during the dialysis treatment until the pH value is not changed.
7. The method for preparing the kelp residue nanocrystalline cellulose using the eutectic solvent and ultrasound according to claim 1, wherein in the step (7), the kelp suspension is subjected to the ultrasonic treatment for 20min, and the pulverizing power of the ultrasonic pulverizer is 650W.
8. The method for preparing the kelp residue nanocrystalline cellulose by using the eutectic solvent and the ultrasound according to claim 1, characterized in that, before the step (1), the following steps are further performed:
(0.1) soaking dried herba Zosterae Marinae in formalin, washing, air drying, pulverizing, sieving, adding Na2CO3Stirring and digesting the water solution, washing, collecting filter residues and drying to obtain non-decalcified kelp residues;
and (0.2) adding the non-decalcified kelp residues obtained in the step (0.1) into an EDTA aqueous solution, stirring, washing and collecting filter residues to obtain kelp residues, and freezing and storing for later use.
9. The method for preparing the kelp residue nanocrystalline cellulose by using the eutectic solvent and the ultrasound according to claim 8, wherein in the step (0.1), the feed-liquid ratio of the added dry kelp to the aqueous formaldehyde solution is 1: 10, the concentration of the formaldehyde aqueous solution is 3.2 wt%, the soaking time is 24h, after being crushed, the kelp powder and the added Na are sieved by a 50-mesh sieve2CO3The feed-liquid ratio of the aqueous solution is 1: 10w/w, Na2CO3The aqueous solution had a concentration of 3 wt% and was digested for 3h with stirring at 50 ℃.
10. The method for preparing the kelp residue nanocrystalline cellulose by using the eutectic solvent and the ultrasound according to claim 8, wherein in the step (0.2), the solid-to-liquid ratio of the added non-decalcified kelp residue to the EDTA aqueous solution is 1: 10w/w, the molar concentration of the EDTA aqueous solution is 0.3mol/L, the stirring time is 2 hours, and the obtained kelp residue is stored at the temperature of below 20 ℃ below zero.
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| 刘振华: "基于新型溶剂的褐藻胶提取剩余物分离及转化研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
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