CN114197233A - Method for separating and extracting cellulose nanofibers from agricultural and forestry solid wastes - Google Patents
Method for separating and extracting cellulose nanofibers from agricultural and forestry solid wastes Download PDFInfo
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Abstract
The invention provides a method for separating and extracting cellulose nanofibers from agricultural and forestry solid wastes, and belongs to the field of separation and extraction of natural high polymer materials. The invention utilizes an acidolysis system consisting of organic acid and organic solvent to treat agricultural and forestry solid waste as a raw material, and prepares the cellulose nano-fiber under the conditions of certain reaction temperature and reaction time. A byproduct generated in the reaction process is glucoside, which is a humectant with excellent performance and can be used in the fields of cosmetics and foods. The method adopts the mode of firstly preparing the fiber nano-fiber and then separating the hemicellulose from the lignin, rather than the mode of firstly separating the hemicellulose and the lignin to obtain the cellulose and then preparing the nano-fiber, which is adopted by the previous researchers. Compared with the prior method, the method has the advantages of energy conservation, environmental protection and simple and convenient process, has the potential of replacing the mainstream preparation mode of the cellulose nano-fiber in the current market, and is easy for industrialized large-scale preparation.
Description
Technical Field
The invention relates to a method for separating and extracting cellulose nanofibers from agricultural and forestry solid wastes, and belongs to the field of separation and extraction of natural high polymer materials.
Technical Field
China is a big agricultural country, and the quantity of agricultural and forestry solid wastes generated by agricultural production activities per year is up to hundreds of millions of tons. The agricultural and forestry solid wastes comprise peanut shells, corn straws, wheat straws, tree sawdust and the like, and the main chemical components of the agricultural and forestry solid wastes comprise 30-50 wt% of cellulose, 15-35 wt% of lignin and 20-45% of hemicellulose, and the content of the three can reach more than 95%. The agriculture and forestry solid wastes are mostly discarded into the surrounding environment except for being used as fuel and coarse fodder, so that the resource is greatly wasted and the environment is seriously polluted, and the development concept of carbon peak reaching and carbon neutralization in China is contrary to. Cellulose is the most abundant natural polymer on earth, and is a linear high-molecular homopolymer consisting of beta-1, 4-glycosidic bonds connected with anhydrous glucose units. The cellulose chains are oriented and held together tightly by hydrogen bonding and van der Waals forces to form elementary fibers, which are further combined to form larger fibrillar structures (Tomas Ross, Hsiao B S, Sderberg L D. cellulose fibers: insulating the Opportunities and changes for nanocell Spinning (Adv. Mater.28/2021) [ J ]. Advanced Materials,2021, 33). The processing and utilization of the agricultural and forestry solid wastes into substitute products of petrochemicals are increasingly paid more and more attention by scientists.
Cellulose Nanofibers (CNFs) are natural polymer nanomaterials prepared from natural biomass raw materials such as cotton, wood, bacterial cellulose and the like, and contain a crystalline region and a non-crystalline region, the diameter of the crystalline region is 10-30 nm, and the length of the crystalline region can be from 500nm to several micrometers. CNFs have the advantages of high strength, biodegradability, low cost, large Young's modulus, good biocompatibility, wide sources and the like, and CNFs are modified and processed to prepare high value-added chemicals such as polymer material reinforcing agents, hydrogels, aerogels, drug carriers and the like (Moon R J, Martini A, Nairn J, et al.
Cellulose nanofibers have gradually moved from the laboratory stage to the industrial stage in recent years (Moon, RJ, Schueneman, et al. overview of Cellulose Nanomaterials, Their catalysts and Applications [ J ] JOM-US,2016), and the main methods for preparing CNFs at present are acid hydrolysis, TEMPO oxidation, mechanical, mechanochemical, enzymatic, etc. The Acid Hydrolysis method mainly adopts inorganic Acid such as sulfuric Acid, hydrochloric Acid and the like with higher concentration, and the Acid seriously corrodes equipment in the preparation process and generates a large amount of wastewater (Manuel A, Gallado-S nchez, Diaz-Vidal T, et al. In addition to inorganic acids, some have also used organic acids to prepare cellulose nanofibers, which also have the above-mentioned problems. The TEMPO oxidation method uses 2,2,6, 6-tetramethylpiperidine oxide and NaBr to oxidize cellulose, so that hydroxyl on C6 is oxidized into carboxyl, and although the prepared nano-fiber has good appearance, TEMPO oxidation reagent has high toxicity and price, cannot be prepared on a large scale and only exists in laboratory stages (Isogai A, Zhou Y. reverse nanocelluloses prepared from TEMPO-oxidized wood cellulose fibers: Nanonenets, nanofibers, and nanocrystals [ J ]. Current Opinion in id State and Materials Science,2019,23 (2)). Mechanical methods include high pressure homogenization, ball milling, etc., which are extremely energy-consuming, have high requirements for equipment, and do not conform to the concept of green chemistry development (Lee H, Man S. mechanical pretreatment of cellulose pulp to product cellulose fibers using a dry grinding method [ J ]. Industrial Crops and Products,2017,104: 179-. Enzymatic hydrolysis methods have the disadvantages of harsh reaction conditions, high cost, long reaction time, etc. (Xiao-Quan Chen, Pang G X, Shen W H, et al. These methods are contrary to green chemistry concepts, and therefore new processes need to be developed to prepare CNFs.
At present, the cellulose nanofiber is prepared by mainly using pure cellulose obtained by respectively removing hemicellulose from a biomass raw material through alkaline cooking and removing lignin through oxidation as a raw material, so that the raw material waste is caused, the energy consumption in the reaction process is increased, and a method for directly preparing the biomass raw material into the cellulose nanofiber is not found.
Disclosure of Invention
Aiming at the problems of high energy consumption, high cost, serious environmental pollution, complex process and the like of the preparation of the cellulose nanofibers in the current market, the invention provides a method for preparing the cellulose nanofibers from agricultural and forestry solid wastes.
The technical scheme of the invention is as follows:
a method for separating and extracting cellulose nanofibers from agricultural and forestry solid wastes comprises the following steps:
cleaning the agricultural and forestry solid waste with deionized water to remove impurities, and naturally drying;
crushing the dried agricultural and forestry solid wastes, screening, and sealing for storage for later use;
adding an organic acid catalyst into an organic solvent, after the organic acid is dissolved in a system, adding agricultural and forestry solid waste powder into the system, reacting for 2-5 hours at the temperature of 90-150 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on the filtrate to obtain glucoside, wherein a filter cake is cellulose nanofiber solid containing lignin and hemicellulose, and washing the solid to be neutral;
dispersing the solid product obtained in the step (3) into an aqueous solution, adding sodium hydroxide, reacting at 60-90 ℃ for 3-6 h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, washing a filter cake which is a cellulose nanofiber solid containing lignin to be neutral;
dispersing the solid product obtained after the alkali treatment in the step (4) into an aqueous solution again, adding sodium chlorite, adjusting the pH value with glacial acetic acid, reacting for 3-6 h at the temperature of 60-90 ℃ for oxidation treatment to remove lignin, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid, and washing the solid to be neutral;
and (6) freeze-drying the product oxidized in the step (5) to obtain the cellulose nanofiber.
Further, in the step (1), the agricultural and forestry solid waste comprises one or more than two mixed biomass raw materials of peanut shells, wheat straws, corn straws, pine sawdust and bamboo powder.
Cellulose surrounds hemicellulose externally, and a large amount of lignin is distributed, so that lignocellulose is extremely dense, and external molecules are difficult to enter between cellulose molecular chains to destroy an internal structure. Under the action of organic acid, specific alcohol solvent and high temperature, cellulose chain and hemicellulose chain are depolymerized to lower molecular weight, most of the crystal area is maintained to produce fine cellulose nanometer fiber, and different kinds of glucoside are produced according to different solvents.
Further, in the step (3), the mass ratio of the organic solvent to the agricultural and forestry solid waste is 10: 1-25: 1, and the used organic solvent is one or a mixture of more than two of ethylene glycol, glycerol, sorbitol and n-butyl alcohol;
further, in the step (3), the mass ratio of the organic acid catalyst to the agricultural and forestry solid waste is 0.2: 1-1.2: 1, and the organic acid is one or a mixture of more than two of p-toluenesulfonic acid, methanesulfonic acid, oxalic acid and naphthalenesulfonic acid.
Further, in the step (4), the mass ratio of the amount of the sodium hydroxide to the amount of the agricultural and forestry solid wastes is 0.6: 1-1.4: 1.
Further, in the step (5), the mass ratio of the amount of the sodium chlorite to the amount of the agricultural and forestry solid wastes is 0.6: 1-1.4: 1, and glacial acetic acid is used for adjusting the pH value to be 3-5.
The invention has the beneficial effects that:
when the method is used for preparing the cellulose nano-fiber, the organic acid and the organic solvent are combined, the acidolysis is carried out on the cellulose inside while the external structure is damaged, the hemicellulose and the lignin do not need to be separated firstly, so that the cellulose structure inside the raw material cannot be damaged too seriously by the acidolysis agent, the length of the prepared cellulose nano-fiber cannot be too short like cellulose nanocrystalline, and an alcohol byproduct, namely glucoside, generated in the reaction process is a humectant rich in hydroxyl, and is used in the fields of cosmetics and foods. Compared with preparation methods such as an acid hydrolysis method, a mechanical method, an enzymolysis method and the like, the method has the advantages of energy conservation, environmental protection and simple and convenient process, has the potential of replacing the mainstream preparation method of the cellulose nano-fiber in the current market, and is easy for industrialized large-scale preparation.
The method abandons the traditional method of preparing the cellulose nanofibers by taking pure cellulose obtained by respectively removing hemicellulose from a biomass raw material through alkaline cooking and removing lignin through oxidation as a raw material, and adopts the method of directly preparing the biomass raw material into a mixture of the cellulose nanofibers, the hemicellulose and the lignin and then separating the hemicellulose and the lignin to obtain the pure cellulose nanofibers. In the traditional mode, the hemicellulose and the lignin are used as barriers of reaction and need to be removed firstly to carry out the next reaction, but the method provided by the invention utilizes the hemicellulose and the lignin as a part for protecting cellulose and acid hydrolysis buffering, reduces the destructive effect of an acid hydrolysis environment on the cellulose, and thus prepares the cellulose nano-fiber with better appearance. Meanwhile, glucoside, a by-product generated by the reaction of an alcohol solvent and agricultural wastes in the alcoholysis process, is a humectant with excellent water retention performance, and the prior method for preparing glucoside by people mostly utilizes crop starch as a raw material, so that the mode of 'competing for grains with human' is not good enough, and the mode for preparing glucoside needs to be improved.
Drawings
Fig. 1 is a transmission electron microscope picture of the cellulose nanofiber prepared in example 7, and it can be seen from the picture that the prepared cellulose nanofiber has a diameter of about 20-30 nm, a length of more than 1um, a larger length-diameter ratio, a better morphology, a better dispersibility between fibers, and an unobvious agglomeration phenomenon.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 2g of p-toluenesulfonic acid as a catalyst, adding 125g of n-butanol as an organic solvent for reaction, after the organic acid is dissolved in the system, weighing 5g of peanut shell solid powder, adding the peanut shell solid powder into the system, reacting for 5 hours at the temperature of 90 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on the filtrate to obtain glucoside, wherein a filter cake is cellulose nanofiber solid containing lignin and hemicellulose, and washing the solid to be neutral;
(4) dispersing the obtained solid product into an aqueous solution, adding 6g of sodium hydroxide, reacting at 90 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 3g of sodium chlorite, adjusting the pH value to 4 by using glacial acetic acid, reacting for 3h at the temperature of 70 ℃ for oxidation treatment to remove lignin, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 2
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 6g of a mixture of p-toluenesulfonic acid and naphthalenesulfonic acid as a catalyst, adding 60g of ethylene glycol as a reaction solvent, after organic acid is dissolved in the system, weighing 5g of peanut shell solid powder and wheat straw solid powder, adding the peanut shell solid powder and the wheat straw solid powder into the system, reacting for 3 hours at the temperature of 100 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on filtrate to obtain glucoside, washing a filter cake to be a cellulose nanofiber solid containing lignin and hemicellulose, and washing the solid to be neutral;
(4) dispersing the obtained solid product into an aqueous solution, adding 6g of sodium hydroxide, reacting at 80 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 6g of sodium chlorite, adjusting the pH value to 6 by using glacial acetic acid, reacting for 4h at the temperature of 80 ℃ for oxidation treatment to remove lignin, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 3
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 4g of methanesulfonic acid as a catalyst, adding 100g of n-butanol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of peanut shell solid powder, adding the peanut shell solid powder into the system, reacting for 6 hours at the temperature of 110 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on the filtrate to obtain glucoside, washing the solid to be neutral, wherein a filter cake is cellulose nanofiber solid containing lignin and hemicellulose;
(4) dispersing the obtained solid product into an aqueous solution, adding 7g of sodium hydroxide, reacting at 70 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 6g of sodium chlorite, adjusting the pH value to 5 by using glacial acetic acid, reacting for 5 hours at the temperature of 90 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 4
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 2g of methanesulfonic acid as a catalyst, adding 60g of glycerol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of pine sawdust solid powder, adding the pine sawdust solid powder into the system, reacting for 6 hours at the temperature of 150 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on filtrate to obtain glucoside, wherein a filter cake is cellulose nanofiber solid containing lignin and hemicellulose, and washing the solid to be neutral;
(4) dispersing the obtained solid product into an aqueous solution, adding 6g of sodium hydroxide, reacting at 70 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 4g of sodium chlorite, adjusting the pH value to 6 by using glacial acetic acid, reacting for 6 hours at the temperature of 70 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 5
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 1g of naphthalenesulfonic acid as a catalyst, adding 70g of sorbitol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of pine sawdust solid powder, adding the pine sawdust solid powder into the system, reacting for 5 hours at the temperature of 150 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on filtrate to obtain glucoside, wherein a filter cake is cellulose nanofiber solid containing lignin and hemicellulose, and washing the solid to be neutral;
(4) dispersing the obtained solid product into an aqueous solution, adding 4g of sodium hydroxide, reacting at 90 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 6g of sodium chlorite, adjusting the pH value to 4 by using glacial acetic acid, reacting for 4h at the temperature of 80 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 6
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 4g of p-toluenesulfonic acid as a catalyst, adding 120g of ethylene glycol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of pine sawdust solid powder, adding the pine sawdust solid powder into the system, reacting for 4 hours at the temperature of 100 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on filtrate to obtain glucoside, wherein a filter cake is cellulose nanofiber solid containing lignin and hemicellulose, and washing the solid to be neutral;
(4) dispersing the obtained solid product into an aqueous solution, adding 5g of sodium hydroxide, reacting at 70 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 4g of sodium chlorite, adjusting the pH value to 6 by using glacial acetic acid, reacting for 5 hours at the temperature of 70 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 7
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 6g of p-toluenesulfonic acid as a catalyst, adding 100g of ethylene glycol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of pine sawdust solid powder, adding the pine sawdust solid powder into the system, reacting for 6 hours at the temperature of 140 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on filtrate to obtain glucoside, washing a filter cake to be cellulose nanofiber solid containing lignin and hemicellulose, and washing the solid to be neutral;
(4) dispersing the obtained solid product into an aqueous solution, adding 5g of sodium hydroxide, reacting at 80 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 5g of sodium chlorite, adjusting the pH value to 4 by using glacial acetic acid, reacting for 3h at the temperature of 90 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 8
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 6g of naphthalenesulfonic acid as a catalyst, adding 120g of sorbitol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of wheat straw solid powder and pine sawdust solid powder, adding the wheat straw solid powder and the pine sawdust solid powder into the system, reacting for 4 hours at the temperature of 100 ℃, cooling and filtering after the reaction is finished, carrying out rotary evaporation on a filtrate to obtain glucoside, washing a filter cake to be neutral, and obtaining a cellulose nanofiber solid containing lignin and hemicellulose;
(4) dispersing the obtained solid product into an aqueous solution, adding 6g of sodium hydroxide, reacting at 70 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 7g of sodium chlorite, adjusting the pH value to 4 by using glacial acetic acid, reacting for 5 hours at the temperature of 70 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 9
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing a mixture of 2g of p-toluenesulfonic acid and oxalic acid as a catalyst, adding 70g of n-butanol as a reaction solvent, after dissolving organic acid in the system, weighing 5g of corn straw solid powder, adding the corn straw solid powder into the system, reacting for 6 hours at the temperature of 140 ℃, cooling and filtering after the reaction is finished, carrying out rotary evaporation on the filtrate to obtain glucoside, washing the solid to be neutral, wherein the filter cake is cellulose nanofiber solid containing lignin and hemicellulose;
(4) dispersing the obtained solid product into an aqueous solution, adding 7g of sodium hydroxide, reacting at 90 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 6g of sodium chlorite, adjusting the pH value to 3 by using glacial acetic acid, reacting for 4h at the temperature of 80 ℃ for oxidation treatment to remove lignin, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 10
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 3g of oxalic acid as a catalyst, adding 50g of a mixture of glycerol and ethylene glycol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of pine sawdust solid powder, adding the pine sawdust solid powder into the system, reacting for 5 hours at the temperature of 90 ℃, cooling and filtering after the reaction is finished, carrying out rotary evaporation on the filtrate to obtain glucoside, washing the solid to be neutral, and obtaining a filter cake which is cellulose nanofiber solid containing lignin and hemicellulose;
(4) dispersing the obtained solid product into an aqueous solution, adding 6g of sodium hydroxide, reacting at 70 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 5g of sodium chlorite, adjusting the pH value to 6 by using glacial acetic acid, reacting for 3h at the temperature of 70 ℃ for oxidation treatment to remove lignin, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 11
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 4g of methanesulfonic acid as a catalyst, adding 80g of sorbitol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of bamboo powder solid powder, adding the bamboo powder solid powder into the system, reacting for 4 hours at the temperature of 130 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on the filtrate to obtain glucoside, washing the solid to be neutral, wherein a filter cake is cellulose nanofiber solid containing lignin and hemicellulose;
(4) dispersing the obtained solid product into an aqueous solution, adding 4g of sodium hydroxide, reacting at 80 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 7g of sodium chlorite, adjusting the pH value to 4 by using glacial acetic acid, reacting for 6 hours at the temperature of 80 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 12
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 4g of naphthalenesulfonic acid as a catalyst, adding 110g of ethylene glycol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of corn straw solid powder, adding the corn straw solid powder into the system, reacting for 5 hours at the temperature of 120 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on the filtrate to obtain glucoside, washing the solid to be neutral, wherein a filter cake is cellulose nanofiber solid containing lignin and hemicellulose;
(4) dispersing the obtained solid product into an aqueous solution, adding 3g of sodium hydroxide, reacting at 90 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 5g of sodium chlorite, adjusting the pH value to 6 by using glacial acetic acid, reacting for 4h at the temperature of 90 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 13
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing a mixture of 2g of p-toluenesulfonic acid, oxalic acid and naphthalenesulfonic acid as a catalyst, adding 70g of glycerol as a reaction solvent, after dissolving organic acid in the system, weighing 5g of corn straw solid powder, adding the corn straw solid powder into the system, reacting for 6 hours at the temperature of 150 ℃, cooling and filtering after the reaction is finished, carrying out rotary evaporation on the filtrate to obtain glucoside, wherein a filter cake is cellulose nanofiber solid containing lignin and hemicellulose, and washing the solid to be neutral;
(4) dispersing the obtained solid product into an aqueous solution, adding 4g of sodium hydroxide, reacting at 70 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 6g of sodium chlorite, adjusting the pH value to 4 by using glacial acetic acid, reacting for 3h at the temperature of 70 ℃ for oxidation treatment to remove lignin, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 14
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 4g of methanesulfonic acid as a catalyst, adding 80g of n-butanol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of corn straw solid powder, adding the corn straw solid powder into the system, reacting for 4 hours at the temperature of 140 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on the filtrate to obtain glucoside, wherein a filter cake is cellulose nano-fiber solid containing lignin and hemicellulose, and washing the solid to be neutral;
(4) dispersing the obtained solid product into an aqueous solution, adding 6g of sodium hydroxide, reacting at 80 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 4g of sodium chlorite, adjusting the pH value to 6 by using glacial acetic acid, reacting for 6 hours at the temperature of 80 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 15
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 3g of oxalic acid as a catalyst, adding 100g of glycerol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of corn straw solid powder, adding the corn straw solid powder into the system, reacting for 3 hours at the temperature of 130 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on the filtrate to obtain glucoside, washing the solid to be neutral, wherein a filter cake is cellulose nano-fiber solid containing lignin and hemicellulose;
(4) dispersing the obtained solid product into an aqueous solution, adding 7g of sodium hydroxide, reacting at 80 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 6g of sodium chlorite, adjusting the pH value to 3 by using glacial acetic acid, reacting for 5 hours at the temperature of 70 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 16
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 1g of naphthalenesulfonic acid as a catalyst, adding 120g of n-butanol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of wheat straw solid powder, adding the wheat straw solid powder into the system, reacting for 3 hours at the temperature of 100 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on the filtrate to obtain glucoside, washing the solid to be neutral, wherein a filter cake is cellulose nano-fiber solid containing lignin and hemicellulose;
(4) dispersing the obtained solid product into an aqueous solution, adding 3g of sodium hydroxide, reacting at 90 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 4g of sodium chlorite, adjusting the pH value to 6 by using glacial acetic acid, reacting for 4h at the temperature of 80 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 17
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 2g of p-toluenesulfonic acid as a catalyst, adding 80g of a mixture of ethylene glycol, glycerol and sorbitol as a reaction solvent, after dissolving organic acid in the system, weighing 5g of wheat straw solid powder, adding the wheat straw solid powder into the system, reacting for 6 hours at 120 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on the filtrate to obtain glucoside, wherein a filter cake is cellulose nanofiber solid containing lignin and hemicellulose, and washing the solid to be neutral;
(4) dispersing the obtained solid product into an aqueous solution, adding 5g of sodium hydroxide, reacting at 80 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 6g of sodium chlorite, adjusting the pH value to 3 by using glacial acetic acid, reacting for 3 hours at the temperature of 90 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 18
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 6g of a mixture of p-toluenesulfonic acid and oxalic acid as a catalyst, adding 100g of sorbitol as a reaction solvent, after organic acid is dissolved in the system, weighing 5g of wheat straw solid powder, adding the wheat straw solid powder into the system, reacting for 4 hours at the temperature of 150 ℃, cooling and filtering after the reaction is finished, carrying out rotary evaporation on the filtrate to obtain glucoside, washing the solid to be neutral, wherein a filter cake is cellulose nanofiber solid containing lignin and hemicellulose;
(4) dispersing the obtained solid product into an aqueous solution, adding 4g of sodium hydroxide, reacting at 70 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 7g of sodium chlorite, adjusting the pH value to 4 by using glacial acetic acid, reacting for 6 hours at the temperature of 80 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 19
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 4g of oxalic acid as a catalyst, adding 90g of ethylene glycol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of wheat straw solid powder, adding the wheat straw solid powder into the system, reacting for 5 hours at the temperature of 120 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on the filtrate to obtain glucoside, washing the solid to be neutral, wherein a filter cake is cellulose nano-fiber solid containing lignin and hemicellulose;
(4) dispersing the obtained solid product into an aqueous solution, adding 5g of sodium hydroxide, reacting at 90 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 6g of sodium chlorite, adjusting the pH value to 3 by using glacial acetic acid, reacting for 5 hours at the temperature of 70 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 20
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 3g of naphthalenesulfonic acid as a catalyst, adding 110g of n-butanol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of bamboo powder solid powder, adding the bamboo powder solid powder into the system, reacting for 6 hours at the temperature of 110 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on the filtrate to obtain glucoside, washing the solid to be neutral, wherein a filter cake is cellulose nano-fiber solid containing lignin and hemicellulose;
(4) dispersing the obtained solid product into an aqueous solution, adding 6g of sodium hydroxide, reacting at 80 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 5g of sodium chlorite, adjusting the pH value to 4 by using glacial acetic acid, reacting for 3h at the temperature of 90 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 21
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing a mixture of 2g of oxalic acid and naphthalenesulfonic acid as a catalyst, adding 50g of glycerol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of bamboo powder solid powder, adding the bamboo powder solid powder into the system, reacting for 3 hours at the temperature of 90 ℃, cooling and filtering after the reaction is finished, carrying out rotary evaporation on the filtrate to obtain glucoside, washing the solid to be neutral, wherein a filter cake is cellulose nanofiber solid containing lignin and hemicellulose;
(4) dispersing the obtained solid product into an aqueous solution, adding 6g of sodium hydroxide, reacting at 90 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 6g of sodium chlorite, adjusting the pH value to 5 by using glacial acetic acid, reacting for 4h at the temperature of 90 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 22
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 5g of methanesulfonic acid as a catalyst, adding 60g of sorbitol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of bamboo powder solid powder, adding the bamboo powder solid powder into the system, reacting for 5 hours at the temperature of 100 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on the filtrate to obtain glucoside, washing the solid to be neutral, wherein a filter cake is cellulose nanofiber solid containing lignin and hemicellulose;
(4) dispersing the obtained solid product into an aqueous solution, adding 6g of sodium hydroxide, reacting at 80 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 7g of sodium chlorite, adjusting the pH value to 5 by using glacial acetic acid, reacting for 5 hours at the temperature of 70 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 23
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 4g of naphthalenesulfonic acid as a catalyst, adding 110g of n-butanol as a reaction solvent, after organic acid is dissolved in a system, weighing 5g of bamboo powder solid powder, adding the bamboo powder solid powder into the system, reacting for 4 hours at the temperature of 140 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on the filtrate to obtain glucoside, washing the solid to be neutral, wherein a filter cake is cellulose nano-fiber solid containing lignin and hemicellulose;
(4) dispersing the obtained solid product into an aqueous solution, adding 6g of sodium hydroxide, reacting at 90 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 4g of sodium chlorite, adjusting the pH value to 4 by using glacial acetic acid, reacting for 6 hours at the temperature of 70 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
Example 24
(1) Washing the raw materials with deionized water to remove impurities, and naturally drying;
(2) air-drying, pulverizing with pulverizer, screening, sealing, and storing;
(3) weighing 1g of p-toluenesulfonic acid as a catalyst, adding 125g of sorbitol as a reaction solvent, after organic acid is dissolved in the system, weighing 5g of peanut shell solid powder, adding the peanut shell solid powder into the system, reacting for 3 hours at the temperature of 130 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on the filtrate to obtain glucoside, wherein a filter cake is cellulose nanofiber solid containing lignin and hemicellulose, and washing the solid to be neutral;
(4) dispersing the obtained solid product into an aqueous solution, adding 6g of sodium hydroxide, reacting at 80 ℃ for 4h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid containing lignin, and washing the solid to be neutral;
(5) dispersing the product obtained after alkali treatment into the aqueous solution again, adding 4g of sodium chlorite, adjusting the pH value to 3 by using glacial acetic acid, reacting for 6 hours at the temperature of 70 ℃ to remove lignin by oxidation treatment, filtering after the reaction is finished, wherein a filter cake is cellulose nanofiber solid, and washing the solid to be neutral;
(6) and (4) freeze-drying the oxidized product to obtain the cellulose nanofiber.
In summary, the preparation method of the cellulose nanofiber disclosed by the invention takes agricultural and forestry solid wastes as raw materials, adopts cleaner organic acid as a reaction catalyst, and can be used as a humectant of cosmetics, wherein a byproduct is glucoside when the cellulose nanofiber is prepared. The preparation method adopts a simpler and more convenient mode, takes cheap and easily-obtained agricultural and forestry solid wastes as reaction raw materials, is environment-friendly, greatly reduces energy consumption, and accords with the development concept of carbon neutralization.
Claims (10)
1. A method for separating and extracting cellulose nanofibers from agricultural and forestry solid wastes is characterized by comprising the following steps:
cleaning the agricultural and forestry solid waste with deionized water to remove impurities, and naturally drying;
crushing the dried agricultural and forestry solid wastes, screening, and sealing for storage for later use;
adding an organic acid catalyst into an organic solvent, after the organic acid is dissolved in a system, adding agricultural and forestry solid waste powder into the system, reacting for 2-5 hours at the temperature of 90-150 ℃, cooling and filtering after the reaction is finished, performing rotary evaporation on the filtrate to obtain glucoside, wherein a filter cake is cellulose nanofiber solid containing lignin and hemicellulose, and washing the solid to be neutral;
dispersing the solid product obtained in the step (3) into an aqueous solution, adding sodium hydroxide, reacting at 60-90 ℃ for 3-6 h for alkali treatment to remove hemicellulose, filtering after the reaction is finished, washing a filter cake which is a cellulose nanofiber solid containing lignin to be neutral;
dispersing the solid product obtained after the alkali treatment in the step (4) into an aqueous solution again, adding sodium chlorite, adjusting the pH value with glacial acetic acid, reacting for 3-6 h at the temperature of 60-90 ℃ for oxidation treatment to remove lignin, filtering after the reaction is finished, wherein a filter cake is a cellulose nanofiber solid, and washing the solid to be neutral;
and (6) freeze-drying the product oxidized in the step (5) to obtain the cellulose nanofiber.
2. The method for separating and extracting cellulose nano-fiber from agricultural and forestry solid waste according to claim 1, wherein the agricultural and forestry solid waste comprises one or more than two mixed biomass raw materials of peanut shell, wheat straw, corn straw, pine sawdust and bamboo powder.
3. The cellulose nanofiber separated and extracted from the agricultural and forestry solid wastes according to claim 1 or 2, wherein the mass ratio of the organic solvent to the agricultural and forestry solid wastes is 10: 1-25: 1, and the used organic solvent is one or a mixture of more than two of ethylene glycol, glycerol, sorbitol and n-butanol.
4. The cellulose nanofiber separated and extracted from the agricultural and forestry solid wastes according to claim 1 or 2, wherein the mass ratio of the organic acid catalyst to the agricultural and forestry solid wastes is 0.2: 1-1.2: 1, and the organic acid is one or more of p-toluenesulfonic acid, methanesulfonic acid, oxalic acid and naphthalenesulfonic acid.
5. The cellulose nanofiber separated and extracted from the agricultural and forestry solid wastes according to claim 3, wherein the mass ratio of the organic acid catalyst to the agricultural and forestry solid wastes is 0.2: 1-1.2: 1, and the organic acid is one or a mixture of more than two of p-toluenesulfonic acid, methanesulfonic acid, oxalic acid and naphthalenesulfonic acid.
6. The cellulose nanofiber separated and extracted from agricultural and forestry solid wastes according to claim 1, 2 or 5, wherein the mass ratio of the amount of sodium hydroxide to the amount of the agricultural and forestry solid wastes is 0.6: 1-1.4: 1.
7. The cellulose nanofiber separated and extracted from agricultural and forestry solid wastes according to claim 3, wherein the mass ratio of the amount of sodium hydroxide to the amount of the agricultural and forestry solid wastes is 0.6: 1-1.4: 1.
8. The cellulose nanofiber separated and extracted from agricultural and forestry solid wastes according to claim 4, wherein the mass ratio of the amount of sodium hydroxide to the amount of the agricultural and forestry solid wastes is 0.6: 1-1.4: 1.
9. The cellulose nanofiber separated and extracted from agricultural and forestry solid wastes according to claim 1, 2, 5 or 7, wherein the mass ratio of the amount of sodium chlorite to the amount of agricultural and forestry solid wastes is 0.6:1 to 1.4:1, and the pH is adjusted to 3 to 5 by glacial acetic acid.
10. The cellulose nanofiber separated and extracted from agricultural and forestry solid wastes according to claim 3, wherein the mass ratio of the amount of sodium chlorite to the amount of agricultural and forestry solid wastes is 0.6:1 to 1.4:1, and the pH is adjusted to 3 to 5 by glacial acetic acid.
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