CN116657434A - Method for extracting nanocellulose from sanding machine flower hair - Google Patents
Method for extracting nanocellulose from sanding machine flower hair Download PDFInfo
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- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 60
- 210000004209 hair Anatomy 0.000 title claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 76
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 40
- 230000003647 oxidation Effects 0.000 claims abstract description 29
- 229920000742 Cotton Polymers 0.000 claims abstract description 21
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 210000002268 wool Anatomy 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims abstract 5
- 238000003756 stirring Methods 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000007788 roughening Methods 0.000 abstract description 26
- 229920002678 cellulose Polymers 0.000 abstract description 22
- 239000001913 cellulose Substances 0.000 abstract description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 8
- 230000008961 swelling Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 210000004027 cell Anatomy 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 206010042674 Swelling Diseases 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 description 3
- 235000021190 leftovers Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002749 Bacterial cellulose Polymers 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 239000005016 bacterial cellulose Substances 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010784 textile waste Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/007—Modification of pulp properties by mechanical or physical means
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The application discloses a method for extracting nanocellulose from the flower and hair of a roughening machine, which comprises the following steps: s1, swelling cotton fiber mill Mao Huamao with dimethyl sulfoxide; s2, performing selective oxidation reaction on the swelled flower and wool by adopting a TEMPO/NaBr/NaClO oxidation system to obtain a mixed solution containing nano cellulose; s3, centrifuging the obtained mixed solution to remove the reaction reagent, and dispersing the precipitate in water; s4, carrying out ultrasonic grinding treatment on the dispersed solution to obtain a nanocellulose suspension. The application adopts DMSO pretreatment to swell the flower and wool fibers, which is beneficial to improving the yield; then preparing nano cellulose by a mode of synergy of a TEMPO oxidation method and an ultrasonic method, wherein the nano cellulose has good solution dispersibility and uniform size, the content of carboxyl can be obviously improved in the oxidation process without changing the polymerization degree of cellulose, and the yield of the nano cellulose can be improved. The method of the application has simple operation and less pollution.
Description
Technical Field
The application belongs to the technical field of nano-cellulose preparation, and relates to a method for extracting nano-cellulose from flower hairs of a roughening machine.
Background
Cellulose is a polysaccharide with the most widespread and highest content in nature, and exists in various organisms such as plants, animals, some bacteria and the like, and is a main component of plant cell walls, and the cellulose content in cotton fibers is close to 100%. Typically, nanocellulose is a cellulose material separated from cellulosic raw materials, with a dimension on the order of nanometers. The nanocellulose has the characteristics of high specific surface area, large length-diameter ratio, biodegradability, reproducibility and the like, has excellent mechanical properties, lower thermal expansion coefficient and good biocompatibility, and has wide application prospects in the fields of composite materials, fine chemical engineering, biological medicines, foods and the like. According to the size, morphology and preparation method, the nanocellulose materials can be divided into: cellulose Nanocrystals (CNCs), cellulose Nanofibers (CNFs), and Bacterial Cellulose (BC). The current method for preparing nanocellulose mainly comprises the following steps: inorganic acid hydrolysis and TEMPO oxidation in chemical methods, high-pressure homogenization and fine grinding in physical methods, enzymatic hydrolysis in biological methods, and the like, and there are also two methods for preparing nanocellulose of a desired size in combination.
Among them, the acid hydrolysis method is simple and convenient to operate, is more commonly used, and generally prepares nano cellulose products with smaller sizes. However, the existing acid hydrolysis method is easy to seriously damage the internal structure of cellulose, limits the application of nanocellulose, and causes environmental pollution due to a large amount of acid waste liquid.
Disclosure of Invention
In order to solve the problems existing in the prior art, the main purpose of the application is to provide a method for extracting nanocellulose from the flower and wool of a roughening machine, which is simple and has less pollution, can prepare nanocellulose with good structure and is beneficial to application.
The application provides a method for extracting nanocellulose from the flower and hair of a roughening machine, which comprises the following steps:
s1, pretreating cotton fiber mill Mao Huamao by using dimethyl sulfoxide to swell the fibers in the cotton fiber mill Mao Huamao;
s2, adopting a TEMPO/NaBr/NaClO oxidation system to carry out selective oxidation reaction on the swelled flower and wool at the temperature of 0-10 ℃ to obtain a mixed solution containing nanocellulose;
s3, centrifuging the obtained mixed solution to remove a reaction reagent, and dispersing a precipitate in water;
s4, carrying out ultrasonic grinding treatment on the dispersed solution to obtain a nanocellulose suspension.
Preferably, step S1 is specifically: mixing cotton fiber mill Mao Huamao with dimethyl sulfoxide at 50-60deg.C, and vacuum filtering to obtain swelled flower hair.
Preferably, in the step S1, the mixing and stirring are magnetic stirring treatment, the stirring speed is 300-600 r/min, and the time is 4-6 h.
Further, in the step S1, the mass-to-volume ratio of the cotton fiber mill Mao Huamao to dimethyl sulfoxide is 1g:0.02 to 0.05L, which can be expressed as mass volume ratio of 2 to 5 percent.
Preferably, step S2 is specifically: dispersing the swelled flower and wool in water in ice water bath, adding NaBr, TEMPO and NaClO, regulating the pH value of the system solution to 10.5-11, performing selective oxidation reaction, and adding absolute ethyl alcohol to stop the reaction to obtain a mixed solution.
Preferably, in the step S2, the concentration of NaBr is 4-6 g/L, the concentration of TEMPO is 0.30-0.35 g/L, and the concentration of NaClO is 40-60%; and hydrochloric acid and sodium hydroxide solution are adopted to adjust the pH value of the system solution.
Preferably, in the step S2, the absolute ethyl alcohol accounts for 3-5% of the system solution.
Preferably, in step S3, the rotational speed of the centrifugal treatment is 5000-8000 rpm, and the solution is treated until the pH is 6-8.
Preferably, step S4 is specifically: and (3) placing the dispersed solution into ultrasonic cell crushing equipment to perform cell crushing treatment for 30-60 min, so as to obtain the nanocellulose suspension.
Preferably, in step S4, the diameter of the horn in the ultrasonic cell disruption apparatus is selected to be 6mm.
Compared with the prior art, the application selects cotton fiber wool generated by a sanding machine working procedure as a raw material to prepare the nanocellulose. The leftovers of each textile processing procedure are low in recycling rate, and are mostly treated in modes of incineration, landfill and the like, so that environmental pollution and resource waste are caused, and if the resources can be effectively recycled, the method has important significance for improving the resource utilization rate and reducing the environmental pollution.
According to the application, the study on recycling of the leftovers in the roughening procedure is selected, and the roughening machine flower wool is more suitable for extracting nanocellulose due to the small size. The size of the roughening machine is millimeter, and crushing treatment is not needed; and the cellulose content in the cotton fiber is highest and is close to 100%, hemicellulose and lignin are not contained, and the step of removing the hemicellulose and the lignin is omitted. Meanwhile, the application adopts dimethyl sulfoxide (DMSO) pretreatment to swell the fiber, so that the oxidation reaction is better carried out, and the yield is improved. After pretreatment, the application adopts a mode of combining a TEMPO oxidation method and an ultrasonic method to prepare the nanocellulose. The nano cellulose solution prepared by the method has good dispersibility and uniform size, the content of carboxyl can be obviously improved in the oxidation process without changing the polymerization degree of cellulose, the yield of nano cellulose can be improved, and in addition, the ultrasonic method is simple to operate and pollution-free, and the environmental protection property of the scheme of the application is further improved.
Drawings
FIG. 1 is a frosted finish Mao Checun of some embodiments of the present application as observed with a microscope;
FIG. 2 is a schematic diagram of the oxidation process mechanism of the TEMPO/NaBr/NaClO oxidation system in an embodiment of the application;
FIG. 3 is a TEM image of nanocellulose prepared in example 1;
FIG. 4 is an infrared spectrum of nanocellulose in example 1;
FIG. 5 is a graph of the finally produced sample in comparative example 2.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present application, the following detailed description of the present application with reference to specific embodiments thereof is provided by way of example and explanation only, and should not be construed as limiting the scope of the present application in any way.
The application provides a method for extracting nanocellulose from the flower and hair of a roughening machine, which comprises the following steps:
s1, pretreating cotton fiber mill Mao Huamao by using dimethyl sulfoxide to swell the fibers in the cotton fiber mill Mao Huamao;
s2, carrying out selective oxidation reaction on the surface of the swelled flower and wool at the temperature of 0-10 ℃ by adopting a TEMPO/NaBr/NaClO oxidation system to obtain a mixed solution containing nanocellulose;
s3, centrifuging the obtained mixed solution to remove a reaction reagent, and dispersing a precipitate in water;
s4, carrying out ultrasonic grinding treatment on the dispersed solution to obtain a nanocellulose suspension.
The method for preparing the nanocellulose is simple and has less pollution, the nanocellulose with good structure can be prepared, the yield is high, and the method is beneficial to application.
The method of the embodiment of the application takes cotton fiber roughening machine flower hair as a preparation raw material, and extracts nano cellulose from the cotton fiber roughening machine flower hair. The raw materials adopted in the embodiment of the application are the leftover roughening machine fur of the roughening procedure in the cotton spinning processing process, and mainly are cotton fibers, and the size of the roughening machine fur is millimeter. Fig. 1 shows a sanding machine Mao Checun of some embodiments of the application, using microscopic observation, wherein one fiber is randomly selected that can be measured, approximately 1 millimeter in length (in millimeters). The roughening machine flower hair is generally directly treated as waste, and the roughening machine flower hair is selected for extracting the nanocellulose, so that the size is relatively smaller, and the nanocellulose is more beneficial to extracting; thus, the textile waste is recycled, the waste of resources is reduced, waste is changed into valuable, the utilization rate of the resources is improved, and the environmental pollution is reduced.
The application comprises dimethyl sulfoxide (DMSO) pretreatment of the flower and hair of a roughening machine; in the specific embodiment of the application, the DMSO solution can be poured into dry flower and hair, and the magnetic stirring treatment is carried out for 4 to 6 hours at 50 to 60 ℃, and the flower and hair is cleaned by adopting a vacuum suction filtration device after the treatment is finished. The main purpose of the DMSO pretreatment is to swell the fiber for the subsequent oxidation reaction. Preferably, the mass-volume ratio of the roughening machine hair to the DMSO solution is 2-5% (the mass-volume ratio represents that if 1g of the roughening machine hair is weighed, the DMSO volume is 20-50 mL).
Wherein, the pretreatment of the flower and wool is preferably carried out in a magnetic stirrer, and the stirring speed can be 300-600 r/min; the dimethyl sulfoxide is used as a swelling agent for pretreatment of the flower and wool, so that the chemical components on the surface can be removed, the fiber can be swelled, the volume of the cellulose becomes large after absorbing the swelling agent, and the intermolecular cohesion is reduced, so that the oxidation reaction can be better carried out, and the yield is improved.
After the swollen flower hair is obtained, the embodiment of the application carries out selective oxidation reaction on the swollen fiber through a 2, 6-tetramethyl piperidine-1-oxygen free radical (TEMPO)/NaBr (sodium bromide)/NaClO (sodium hypochlorite) oxidation system. The oxidation reaction in the specific embodiment of the application is preferably carried out in an ice-water bath, the swelled flower and wool is dissolved in water, the swelled flower and wool are uniformly dispersed for 10 to 15 minutes under magnetic stirring, and then the reagent is added: sequentially adding NaBr and TEMPO, and dropwise adding NaClO solution; after stirring evenly, the pH value of the solution is regulated to 10.5-11. And (3) after a certain time of oxidation reaction, adding absolute ethyl alcohol to thoroughly stop the reaction. Preferably, the concentration of NaBr is 4-6 g/L, the concentration of TEMPO is 0.30-0.35 g/L, and the mass concentration of NaClO is 40-60%; the dosage of the absolute ethyl alcohol is 3-5%. The percentages of the sodium hypochlorite and the absolute ethyl alcohol are mass percent (wt%) and are based on the solution.
In the present application, the temperature of the selective oxidation reaction is controlled to be between 0 and 10 ℃. The ice water bath is realized by adding ice cubes or ice bags into the water bath, and the temperature of the water bath can be better controlled by adopting the ice cubes or the ice bags, so that the oxidation reaction is ensured. Wherein the pH value of the reaction system solution is regulated by adopting hydrochloric acid solution and sodium hydroxide solution, and the concentration of the hydrochloric acid and the sodium hydroxide solution is 5-10%. The oxidation reaction is carried out in a magnetic stirrer, and the stirring speed is 300-600 r/min. Here, 5 to 10% hydrochloric acid and sodium hydroxide are prepared by preparing 5 to 10% by weight of hydrochloric acid and sodium hydroxide solution, and adjusting the pH with the prepared solution.
According to the embodiment of the application, the mixed solution containing the nanocellulose is obtained through selective oxidation reaction. In the specific embodiment of the application, the mixed solution after oxidation is preferably subjected to centrifugal treatment by adopting a high-speed centrifugal machine, the supernatant is poured after the centrifugal treatment is finished, and deionized water can be added to continue the centrifugal treatment until the pH value of the solution is neutral; and pouring out the supernatant after centrifugation, leaving a precipitate, and adding a proper amount of deionized water and stirring uniformly.
In the preparation method according to the foregoing embodiment, the centrifugation is specifically a high-speed centrifuge centrifuging at a rotation speed of 5000 to 8000rpm for 10 minutes. Wherein the solution is near neutral or neutral after 3-5 times of centrifugal treatment, and the pH value is between 6 and 8.
Finally, the obtained solution is subjected to ultrasonic pulverization treatment to obtain the nanocellulose suspension. Specifically, the embodiment of the application puts the nanocellulose solution after centrifugal treatment into an ultrasonic cell grinder for cell grinding treatment, the power is set to be 50%, the ultrasonic treatment is carried out for 30-60 min, and the obtained nanocellulose suspension is put into a refrigerator for storage and use. Wherein, the diameter of the amplitude transformer of the ultrasonic cell grinder is 6mm; the selection of the amplitude transformer is related to the dosage of the solution, and the 10-100mL of the solution is 6mm of the amplitude transformer, so that the effect is good.
According to the embodiment of the application, the nano cellulose is prepared by adopting a mode of synergy of a TEMPO oxidation method and an ultrasonic method; selectively oxidizing cellulose primary hydroxyl by a TEMPO chemical oxidation method, wherein the oxidation reaction occurs on the surface of the microfiber, and carboxyl and aldehyde groups are introduced; the TEMPO oxidation process can not change the fiber morphology and crystallinity, so the application carries out ultrasonic pulverization treatment after the TEMPO oxidation reaction, and the cellulose cell wall is peeled off and gradually decomposed into cellulose nanofiber products by the fluid shearing force generated by an instrument and the jet flow of high-speed impinging liquid.
The selective oxidation process in some embodiments of the present application is schematically shown in fig. 2, and fig. 2 is a schematic diagram of the oxidation process mechanism of the TEMPO/NaBr/NaClO oxidation system in the embodiments of the present application. Wherein the hydroxyl groups of the cellulose primary alcohols are selectively oxidized and converted into aldehyde groups and carboxyl groups, and the carboxyl groups can be formed into sodium salt with NaOH under the condition of pH=10.
The embodiment of the application can recycle the waste flower and wool in the roughening process in the cotton spinning process in the factory, thereby solving the problem of resource waste; the cellulose is fully swelled after the DMSO pretreatment, the oxidation reaction is more thoroughly carried out, and the yield is improved. The nano cellulose solution prepared by the method has good dispersibility and uniform size, and the diameter of a finished product can be between 10 and 30 nm; the oxidation process of the embodiment of the application can obviously improve the content of carboxyl without changing the polymerization degree of cellulose, can improve the yield of nano cellulose, and has the characteristics of simple operation, no pollution and the like, and is suitable for large-scale popularization.
The present application will be described in further detail with reference to the following examples and drawings, the examples described herein only assist in understanding the present application, and the embodiments of the present application are not limited thereto. Wherein, the cellulose raw material is from waste cotton fibers of flower wool produced by a roughening machine in the cotton spinning process, and the size is in millimeter level; the rest raw materials are all commercially available, and conventional processing equipment is adopted, wherein the diameter of an amplitude transformer of the ultrasonic cell grinder is 6mm.
Example 1
The preparation method of the nanocellulose comprises the following steps:
(1) Pretreatment of frosted machine flower hair DMSO
Weighing 1g of the flower and hair of the roughening machine, adding 30mL of DMSO solution, magnetically stirring at 60 ℃ for 3h,300r/min, cleaning the flower and hair by adopting a vacuum suction filtration device, and filtering the DMSO solution;
(2) TEMPO oxidation process
Placing the prepared ice bag into a water bath kettle, controlling the water bath temperature to be 10 ℃, dissolving the pretreated flower wool into 60mL of water, and placing the water bath kettle into a magnetic stirrer for stirring for 300r/min and 10min; then sequentially adding 0.6g NaBr and 0.032g TEMPO, weighing 40mL NaClO, dropwise adding the mixture into the reaction solution by using a dropper, uniformly stirring, adjusting the pH of the solution by using a hydrochloric acid solution, adjusting the pH to 10.5, finishing the oxidation reaction after 3 hours, and adding 5mL absolute ethyl alcohol to completely stop the reaction;
(3) Centrifugal treatment
Centrifuging the oxidized solution by adopting a high-speed centrifuge, centrifuging at a rotation speed of 5000rpm for 10min, pouring out supernatant, adding deionized water for further centrifuging for 3 times, centrifuging until the pH is neutral, pouring out supernatant, leaving precipitate, adding a proper amount of deionized water, and stirring uniformly;
(4) Ultrasonic treatment
And (3) placing the centrifuged nanocellulose solution into an ultrasonic cell grinder, grinding, setting the power to be 50%, and carrying out ultrasonic treatment for 30min to obtain nanocellulose suspension. The ultrasonic cell grinder used in this experiment had a power of 650w and 50% 325w.
The nanocellulose yield was calculated to be 50% by freeze-drying the nanocellulose solution. The finished product diameter is between 10 and 30nm (calculated by Image J software according to figure 3, and figure 3 is a TEM Image of nanocellulose) through observation and analysis of a Transmission Electron Microscope (TEM), and the nanocellulose has small size discreteness and good size uniformity. As can be seen from the infrared spectrogram of FIG. 4, the DMSO pretreatment does not damage the structure of cellulose, and the TEMPO/NaBr/NaClO oxidation system oxidizes primary alcohol hydroxyl groups in cellulose macromolecules into carboxyl groups.
Example 2
The preparation method of the nanocellulose comprises the following steps:
(1) Pretreatment of frosted machine flower hair DMSO
Weighing 3g of the flower and hair of the roughening machine, adding 150mL of DMSO solution, magnetically stirring at 60 ℃ for 4 hours and 400r/min, cleaning the flower and hair by adopting a vacuum suction filtration device, and filtering the DMSO solution;
(2) TEMPO oxidation treatment
Placing the prepared ice bag into a water bath kettle, controlling the water bath temperature to be 10 ℃, dissolving the pretreated flower wool into 210mL of water, and placing the water bath kettle into a magnetic stirrer to stir for 400r/min and 15min; sequentially adding 1.8g NaBr and 0.096g TEMPO, weighing 90mL NaClO, dropwise adding into the reaction solution by using a dropper, uniformly stirring, adjusting the pH of the solution by using a hydrochloric acid solution, adjusting the pH to 10.5, finishing the oxidation reaction after 3 hours, and adding 15mL absolute ethyl alcohol to completely stop the reaction;
(3) Centrifugal treatment
Centrifuging the oxidized solution by adopting a high-speed centrifuge, centrifuging at 6000rpm for 10min, pouring out the supernatant, adding deionized water for further centrifuging for 5 times, centrifuging until the pH is neutral, pouring out the supernatant, leaving a precipitate, adding a proper amount of deionized water, and stirring uniformly;
(4) Ultrasonic treatment
And (3) placing the centrifuged nanocellulose solution into an ultrasonic cell grinder, grinding, setting the power to be 50%, and carrying out ultrasonic treatment for 40min to obtain nanocellulose suspension.
The diameter of the finished product is between 10 and 30nm through observation and analysis by a transmission electron microscope.
Example 3
The preparation method of the nanocellulose comprises the following steps:
(1) Pretreatment of frosted machine flower hair DMSO
Weighing 5g of the flower and hair of the roughening machine, adding 250mL of DMSO solution, magnetically stirring at 60 ℃ for 5h,500r/min, cleaning the flower and hair by adopting a vacuum suction filtration device, and filtering the DMSO solution;
(2) TEMPO oxidation treatment
Placing the prepared ice bag into a water bath kettle, controlling the water bath temperature to be 10 ℃, dissolving the pretreated flower wool into 400mL of water, and placing the water bath kettle into a magnetic stirrer to stir for 500r/min and 15min; then sequentially adding 3g NaBr and 0.16g TEMPO, weighing 100mL NaClO, dropwise adding into the reaction solution by using a dropper, stirring uniformly, adjusting the pH of the solution by using a hydrochloric acid solution, adjusting the pH to 10.5, finishing the oxidation reaction after 3h, and adding 25mL absolute ethyl alcohol to completely stop the reaction;
(3) Centrifugal treatment
Centrifuging the oxidized solution by adopting a high-speed centrifuge, centrifuging for 10min at a rotation speed of 8000rpm, pouring out supernatant, adding deionized water for further centrifuging for 5 times, centrifuging until the pH is neutral, pouring out supernatant, leaving precipitate, adding a proper amount of deionized water, and stirring uniformly;
(4) Ultrasonic treatment
And (3) placing the centrifuged nanocellulose solution into an ultrasonic cell grinder, grinding, setting the power to be 50%, and carrying out ultrasonic treatment for 60min to obtain nanocellulose suspension.
The diameter of the finished product is between 10 and 30nm through observation and analysis by a transmission electron microscope.
The different processes of the above examples can all obtain nanocellulose suspensions with comparable sizes. Wherein, as the oxidation reaction proceeds, the pH of the solution is adjusted by sodium hydroxide solution, so that the pH of the solution is kept at about 10 until the pH of the solution is reduced, the reaction is completed, the whole process is continued for about 3 hours, and then absolute ethyl alcohol is added to thoroughly stop the reaction.
Comparative example 1
The preparation method of the nanocellulose of the comparative example comprises the following steps:
(1) TEMPO oxidation process
Placing the prepared ice bag into a water bath kettle, controlling the water bath temperature to be 10 ℃, dissolving the flower and wool of a roughening machine into 60mL of water, and placing the water bath kettle into a magnetic stirrer for stirring for 300r/min and 10min; then sequentially adding 0.6g NaBr and 0.032g TEMPO, weighing 40mL NaClO, dropwise adding the mixture into the reaction solution by using a dropper, uniformly stirring, adjusting the pH of the solution by using a hydrochloric acid solution, adjusting the pH to 10.5, finishing the oxidation reaction after 3 hours, and adding 5mL absolute ethyl alcohol to completely stop the reaction;
(2) Centrifugal treatment
Centrifuging the oxidized solution by adopting a high-speed centrifuge, centrifuging at a rotation speed of 5000rpm for 10min, pouring out supernatant, adding deionized water for further centrifuging for 3 times, centrifuging until the pH is neutral, pouring out supernatant, leaving precipitate, adding a proper amount of deionized water, and stirring uniformly;
(3) Ultrasonic treatment
And (3) placing the centrifuged nanocellulose solution into an ultrasonic cell grinder, grinding, setting the power to be 50%, and carrying out ultrasonic treatment for 30min to obtain nanocellulose suspension.
The diameter of the finished product is between 10 and 30nm through observation and analysis by a transmission electron microscope.
The nanocellulose suspension was freeze-dried and the yield calculated to be smaller than the example with DMSO solution swelling treatment.
Comparative example 2
The preparation method of the nanocellulose of the comparative example comprises the following steps:
(1) Pretreatment of frosted machine flower hair DMSO
Weighing 1g of the flower and hair of the roughening machine, adding 30mL of DMSO solution, magnetically stirring at 60 ℃ for 3h,300r/min, cleaning the flower and hair by adopting a vacuum suction filtration device, and filtering the DMSO solution;
(2) TEMPO oxidation process
Placing the prepared ice bag into a water bath kettle, controlling the water bath temperature to be 10 ℃, dissolving the pretreated flower wool into 60mL of water, and placing the water bath kettle into a magnetic stirrer for stirring for 300r/min and 10min; then sequentially adding 0.6g NaBr and 0.032g TEMPO, weighing 40mL NaClO, dropwise adding the mixture into the reaction solution by using a dropper, uniformly stirring, adjusting the pH of the solution by using a hydrochloric acid solution, adjusting the pH to 10.5, finishing the oxidation reaction after 3 hours, and adding 5mL absolute ethyl alcohol to completely stop the reaction;
(3) Centrifugal treatment
Centrifuging the oxidized solution by adopting a high-speed centrifuge, centrifuging at a rotation speed of 5000rpm for 10min, pouring out supernatant, adding deionized water for further centrifuging for 3 times, centrifuging until the pH is neutral, pouring out supernatant, leaving precipitate, adding a proper amount of deionized water, and stirring uniformly;
comparison without ultrasonic cell disruption treatment, for example as shown in fig. 5, shows that TEMPO oxidation alone does not alter fiber morphology and does not form a stable nanocellulose suspension.
From the above examples, the nanocellulose is prepared by using the flower and hair of the roughening machine as a raw material, performing DMSO swelling pretreatment, and adopting a mode of combining a TEMPO oxidation method and an ultrasonic method. The nano cellulose solution prepared by the method has good dispersibility and uniform size, the content of carboxyl can be obviously improved in the oxidation process without changing the polymerization degree of cellulose, the yield of nano cellulose can be improved, and in addition, the ultrasonic method has simple operation, no pollution and good environmental protection.
Finally, it should be noted that the specific embodiments described herein are merely illustrative of the spirit of the application and are not limiting of the application. Other modifications and additions to the described embodiments and similar alternatives to the described embodiments will be apparent to those skilled in the art, and it is not necessary nor necessary to fully implement the application. While these obvious variations and modifications, which come within the spirit of the application, are within the scope of the application, they are to be construed as being without departing from the spirit of the application.
Claims (10)
1. The method for extracting the nanocellulose from the sanding machine flower hair is characterized by comprising the following steps of:
s1, pretreating cotton fiber mill Mao Huamao by using dimethyl sulfoxide to swell the fibers in the cotton fiber mill Mao Huamao;
s2, adopting a TEMPO/NaBr/NaClO oxidation system to carry out selective oxidation reaction on the swelled flower and wool at the temperature of 0-10 ℃ to obtain a mixed solution containing nanocellulose;
s3, centrifuging the obtained mixed solution to remove a reaction reagent, and dispersing a precipitate in water;
s4, carrying out ultrasonic grinding treatment on the dispersed solution to obtain a nanocellulose suspension.
2. The method according to claim 1, wherein step S1 is specifically: mixing cotton fiber mill Mao Huamao with dimethyl sulfoxide at 50-60deg.C, and vacuum filtering to obtain swelled flower hair.
3. The method according to claim 2, wherein in step S1, the mixing and stirring are magnetic stirring, the stirring speed is 300-600 r/min, and the time is 4-6 h.
4. A method according to claim 3, wherein in step S1, the mass to volume ratio of the cotton fiber mill Mao Huamao to dimethyl sulfoxide is 1g: 0.02-0.05L.
5. The method according to claim 2, wherein step S2 is specifically: dispersing the swelled flower and wool in water in ice water bath, adding NaBr, TEMPO and NaClO, regulating the pH value of the system solution to 10.5-11, performing selective oxidation reaction, and adding absolute ethyl alcohol to stop the reaction to obtain a mixed solution.
6. The method according to claim 5, wherein in step S2, the concentration of NaBr is 4-6 g/L, the concentration of TEMPO is 0.30-0.35 g/L, and the concentration of NaClO is 40-60%; and hydrochloric acid and sodium hydroxide solution are adopted to adjust the pH value of the system solution.
7. The method according to claim 6, wherein in the step S2, the absolute ethyl alcohol accounts for 3-5% of the system solution.
8. The method according to any one of claims 2 to 7, wherein in step S3, the centrifugal treatment is carried out at a rotational speed of 5000 to 8000rpm until the solution pH is 6 to 8.
9. The method according to claim 8, wherein step S4 is specifically: and (3) placing the dispersed solution into ultrasonic cell crushing equipment to perform cell crushing treatment for 30-60 min, so as to obtain the nanocellulose suspension.
10. The method of claim 9 wherein in step S4 the horn diameter in the ultrasonic cell comminution apparatus is selected to be 6mm.
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