CN116446213B - Enteromorpha-based cellulose nanofiber, preparation method and application - Google Patents
Enteromorpha-based cellulose nanofiber, preparation method and application Download PDFInfo
- Publication number
- CN116446213B CN116446213B CN202310670135.8A CN202310670135A CN116446213B CN 116446213 B CN116446213 B CN 116446213B CN 202310670135 A CN202310670135 A CN 202310670135A CN 116446213 B CN116446213 B CN 116446213B
- Authority
- CN
- China
- Prior art keywords
- enteromorpha
- cellulose nanofiber
- based cellulose
- solution
- drying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 123
- 239000001913 cellulose Substances 0.000 title claims abstract description 123
- 241000196252 Ulva Species 0.000 title claims abstract description 102
- 239000002121 nanofiber Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002028 Biomass Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 11
- 239000002537 cosmetic Substances 0.000 claims abstract description 6
- 239000011208 reinforced composite material Substances 0.000 claims abstract description 6
- 239000003973 paint Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 22
- 239000000523 sample Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 10
- 238000004061 bleaching Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 241000196253 Ulva prolifera Species 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000013535 sea water Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 230000001939 inductive effect Effects 0.000 claims 1
- 238000011282 treatment Methods 0.000 abstract description 18
- 239000003513 alkali Substances 0.000 abstract description 10
- 229920001046 Nanocellulose Polymers 0.000 abstract description 8
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 5
- 238000004806 packaging method and process Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 239000008204 material by function Substances 0.000 abstract 2
- 238000000605 extraction Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002604 ultrasonography Methods 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 241000195493 Cryptophyta Species 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000944 Soxhlet extraction Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241001474374 Blennius Species 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000005115 demineralization Methods 0.000 description 3
- 230000002328 demineralizing effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000005476 size effect Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000003306 harvesting Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 241000195628 Chlorophyta Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 241000196246 Ulvaceae Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000013178 mathematical model Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- 238000009898 sodium hypochlorite bleaching Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
- D21B1/00—Fibrous raw materials or their mechanical treatment
- D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
- D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
- D21B1/30—Defibrating by other means
- D21B1/306—Defibrating by other means using microwaves
-
- 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
- D21C1/00—Pretreatment of the finely-divided materials before digesting
- D21C1/06—Pretreatment of the finely-divided materials before digesting with alkaline reacting 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
- 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
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Mechanical Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses an enteromorpha-based cellulose nanofiber, a preparation method and application thereof, wherein the cellulose nanofiber is rapidly prepared in a mode of combining microwave-assisted alkali treatment and high-strength ultrasonic treatment, the preparation process is green and efficient, the prepared cellulose nanofiber has a cellulose crystal structure and typical characteristic peaks of nanocellulose, is natural and pollution-free, has uniform size, large length-diameter ratio, high strength and good stability, and can realize high-value utilization of waste enteromorpha; the cellulose nanofiber prepared by the invention can be applied to various functional materials such as reinforced composite materials, paper products, packaging products, cosmetics, paints/coatings, biomedical materials and the like, and aims to regulate and control rheological property and stability of the cellulose nanofiber, so that the application of biomass-based high-added-value products is widened, and a green and sustainable road is provided for developing novel functional materials.
Description
Technical Field
The invention relates to the technical field of preparation of environment-friendly degradable compounds for recycling solid wastes, in particular to a preparation method and application of enteromorpha-based cellulose nanofiber based on microwave-assisted pretreatment and high-intensity ultrasound.
Background
Cellulose is the most abundant natural polymer and renewable material in nature, and has the advantages of low cost, abundant sources and environmental friendliness. Renewable and sustainable nanomaterials are increasingly receiving attention from researchers as society progresses. Therefore, the nanocellulose becomes an option in the nanomaterial on the earth, is taken as a nano functional material extracted from cellulose, has the characteristics of high Young modulus, high tensile strength, high length-diameter ratio, large specific surface area, small size effect, high reactivity and the like, simultaneously maintains the benefit of the natural cellulose which is renewable, biodegradable, environment-friendly and rich in source, and is widely applied to the fields of foods, cosmetics, pharmacy and the like.
The initial preparation method of the cellulose nanofiber mainly adopts mechanical treatment, wherein the high-pressure homogenization method is a method for preparing the nanocellulose by completely utilizing mechanical action for the first time in the world, however, the preparation method needs to consume a large amount of energy, has higher requirements on machine equipment, has high cost, is easy to block the equipment, and is not beneficial to popularization and use. The prior method is to adopt a combined treatment mode, namely a pretreatment cooperative mechanical treatment mode. The pretreatment can not only greatly reduce the energy consumption and the dosage of chemicals, but also produce cellulose nanofiber products with different functional groups. In general, different pretreatments can be used to weaken the cellulosic fibrous structure, promote fibrillation of the fibers, and thereby reduce energy consumption.
Nanocellulose is in a conventional sense mainly dependent on lignocellulosic raw materials of terrestrial plants, such as wood, beans, cotton, sugarcane, straw, coffee peel, banana peel, etc. However, with the shortage of energy and food, marine biomass is considered as a potential source, and extraction of nanocellulose from macroalgae and application thereof in polymer composites are hot spots of research in recent years. Macroalgae have become a potential source of nanocellulose material production due to several advantages of their own: (1) the content of other polysaccharide which is used for interfering the separation of cellulose is low, and the cellulose is easy to extract; (2) algae have high carbohydrate content; (3) compared with other sources, the method does not need to occupy cultivated land and chemical fertilizer, has wide sources and reduces the harvesting time due to rapid growth; (4) the lignin content is low and extraction results in a purer cellulosic component.
Enteromorpha prolifera is derived from Ulvaceae of Chlorophyta and is widely distributed in the east China sea and yellow sea. The enteromorpha is strong in adaptability and reproductive capacity, and can be propagated in a large quantity in a short time. In recent years, along with global climate change and water eutrophication, enteromorpha frequently bursts in Shandong and Jiangsu sea areas, floats and gathers to the shore, decays and stinks, pollutes the environment and seriously threatens the development of coastal fishery and travel industry. The enteromorpha is mainly buried in a treatment mode, but is not really and effectively utilized, and if the enteromorpha can be processed and utilized, the inundated enteromorpha becomes a rich resource. In view of the high cellulose content in the enteromorpha cell walls, the extraction is easy, and the cellulose extract has a loose reticular structure, a larger specific surface area and good performance in the aspects of water absorption, physical and mechanical properties. Therefore, the extraction process of the enteromorpha cellulose is greatly developed and used for preparing the functional material, waste is changed into valuable, and the realization of the resource utilization of the enteromorpha has a wide application prospect.
Chinese patent application CN111893789a discloses a preparation method and application of nanofibrillated cellulose, the method optimizes and upgrades the original method, and comprises the steps of ethanol soxhlet extraction to remove lipid, sodium hydroxide alkali treatment to remove protein, glacial acetic acid and sodium hypochlorite bleaching, hydrochloric acid demineralization and ultrasonic oscillation, and the nanofibrillated cellulose is obtained by successful extraction and separation. However, the method has the limitation factors of long Soxhlet extraction and degreasing time, extremely corrosive sodium hypochlorite, poor mechanical stripping effect of ultrasonic oscillation and the like.
The invention takes waste algae enteromorpha as the raw material to prepare the cellulose nanofiber, realizes the functionalization and high-performance wide application in the field, is beneficial to the utilization of waste algae, the development of biomass resources and the protection of ecological environment, and realizes the sustainable development of economy.
Disclosure of Invention
In view of the above, the invention provides a preparation method and application of enteromorpha-based cellulose nanofiber based on microwave-assisted pretreatment and high-intensity ultrasound, and the preparation method of enteromorpha-based cellulose nanofiber not only can change enteromorpha polluting the environment into valuables, but also can relieve energy consumption, and can improve the extraction process of cellulose nanofiber, thereby achieving the purposes of reducing energy consumption and environment-friendly extraction process, and extracting cellulose nanofiber with stable performance and uniform size.
Specifically, the invention provides a preparation method of enteromorpha-based cellulose nanofiber, which is characterized by comprising the following steps:
step 1: washing the collected fresh enteromorpha in natural seawater for several times, preserving at low temperature, repeatedly washing with water to remove precipitate impurities, drying, and pulverizing into enteromorpha powder;
step 2: taking enteromorpha powder, and carrying out sodium hydroxide pretreatment under microwave irradiation to induce biomass dewaxing;
step 3: placing dewaxed enteromorpha powder into hydrogen peroxide solution, heating and bleaching, removing pigment, centrifugally washing with distilled water until the solution is neutral, and drying;
step 4: suspending insoluble components in hydrochloric acid solution, heating to boiling, cooling, stirring the solution, centrifuging to remove supernatant, and washing with deionized water for multiple times until the solution is neutral;
step 5: the suspension is decomposed into cellulose nanofibers by ultrasonic action in a high-strength ultrasonic probe, and the cellulose nanofibers are collected and freeze-dried.
In some specific embodiments of the present invention, the drying in step 1 is air drying at 60 ℃ in a forced air drying oven, and the crushing in step 1 is crushing enteromorpha into fine powder by using a crusher, and sieving with 100 mesh sieve.
In some embodiments of the present invention, the specific operation steps of step 2 are: under the irradiation of 360W microwaves, the enteromorpha powder is heated by microwaves, and NaOH solution is added for pretreatment to induce dewaxing of biomass; the solid-to-liquid ratio of the enteromorpha powder to the NaOH solution is 1:5-1:10 (w/v), the concentration of the NaOH solution is 1.0-3.0M, and the time is 20-90min; the insoluble components are washed for a plurality of times by hot water, centrifuged for a plurality of times until the pH value of the solution is neutral, and freeze-dried and stored.
In some embodiments of the invention, the microwave heating time in step 2 is 30 minutes.
In some embodiments of the invention, the concentration of NaOH solution in step 2 is 2.5M; the solid-to-liquid ratio of the enteromorpha powder to the NaOH solution is 1:8 (w/v).
In some embodiments of the invention, the centrifugation parameters in step 2 are 4000rpm for 15min.
In some embodiments of the present invention, the specific operation steps of step 3 are: placing dewaxed enteromorpha powder into hydrogen peroxide solution with the concentration of 3%, wherein the solid-to-liquid ratio of the enteromorpha powder to the hydrogen peroxide solution is 1:6-1:12 (w/v); heating and bleaching at 70-90 ℃ for 5.5-10h; after cooling to room temperature, centrifuging for 10-20min, centrifuging for several times, discarding supernatant, washing insoluble components with water to neutral pH, and freeze drying for preservation.
In some embodiments of the invention, the solid-to-liquid ratio of the enteromorpha powder to the hydrogen peroxide solution in step 3 is 1:8 (w/v).
In some embodiments of the invention, the heated bleaching temperature in step 3 is 80 ℃ for a period of 6 hours.
In some embodiments of the invention, the centrifugation speed in step 3 is 4000rpm and centrifugation is carried out for 15min.
In some embodiments of the present invention, the specific operation steps of step 4 are: suspending insoluble components in 3-8% hydrochloric acid solution, heating to 100deg.C for 5-15min; cooling to 30deg.C, maintaining at the temperature for 14-24 hr, centrifuging for 10min, centrifuging for several times, and removing supernatant; the insoluble components were washed with water several times until the pH of the solution was neutral, and stored by freeze drying.
In some embodiments of the invention, the concentration of the dilute hydrochloric acid in step 4 is 5%.
In some embodiments of the invention, the solid to liquid ratio in step 4 is 1:5 (w/v).
In some embodiments of the invention, the heating time in step 4 is 10 minutes.
In some embodiments of the invention, step 4 is cooled to 30 ℃ and then maintained at that temperature for 16 hours.
In some embodiments of the invention, the centrifugation speed in step 4 is 4000rpm.
In some embodiments of the present invention, the specific operation steps of step 5 are: dissolving a freeze-dried sample in water, preparing water suspension with the concentration of 0.2-1%, placing the suspension into a high-intensity ultrasonic probe with the probe frequency of 1200W, the probe frequency of 70-95%, an ice bath environment and the ultrasonic time of 0.5-2h, and freeze-drying and preserving the suspension to obtain the enteromorpha cellulose nanofiber.
In some embodiments of the invention, the concentration in step 5 is 0.5% and the magnetic stirring time is 1h.
In some embodiments of the invention, the high intensity ultrasound is based on the cavitation effect principle of ultrasound.
In some embodiments of the invention, the water in steps 1-5 is deionized water.
The invention also provides enteromorpha-based cellulose nanofiber which is prepared by the preparation method of the enteromorpha-based cellulose nanofiber.
In some embodiments of the invention, the enteromorpha-based cellulose nanofiber has a diameter in the range of 10-30nm and a length of 1-10 μm.
In some embodiments of the invention, the enteromorpha-based cellulose nanofiber has an average diameter of 25.7nm and an average length of 4.5 μm.
In some embodiments of the invention, enteromorpha-based cellulose nanofibers have an aspect ratio of 120-310.
In some embodiments of the invention, the enteromorpha-based cellulose nanofiber has a crystallinity index of 55-65%.
In some embodiments of the invention, the enteromorpha-based cellulose nanofibers exhibit a characteristic peak of cellulose i.
In some embodiments of the invention, the enteromorpha-based cellulose nanofiber has a low inorganic content and an ash content of 0.7-2.6%.
In some embodiments of the invention, the thermal main degradation zone of the enteromorpha-based cellulose nanofiber is 251.4-372.3 ℃ and the maximum thermal degradation temperature is 345 ℃.
In some embodiments of the invention, the enteromorpha-based cellulose nanofiber yield is 11.4-15.1% of the dry biomass.
The invention also provides an application of the enteromorpha-based cellulose nanofiber prepared by the preparation method of the enteromorpha-based cellulose nanofiber in preparation of reinforced composite materials, paper products, packaging products, cosmetics, paints, coatings and biomedical materials.
The invention also provides a reinforced composite material, a paper product, a packaging product, a cosmetic, a coating or a biomedical material, which comprises the enteromorpha-based cellulose nanofiber prepared by the preparation method of the enteromorpha-based cellulose nanofiber.
Compared with the prior art, the invention has the following remarkable advantages and effects:
according to the invention, enteromorpha is used as a raw material, cellulose nanofibers are extracted from enteromorpha, and the inundated enteromorpha becomes rich resources, so that the recycling of the enteromorpha is realized.
The enteromorpha as an extraction raw material is algae, so that the enteromorpha as the extraction raw material becomes a potential production source of nano cellulose materials, and the extraction advantage is more obvious: (1) the content of other polysaccharide which is used for interfering the separation of cellulose is low, and the cellulose is easy to extract; (2) algae have high carbohydrate content; (3) compared with other sources, the method does not need to occupy cultivated land and chemical fertilizer, has wide sources and reduces the harvesting time due to rapid growth; (4) the lignin content is low and extraction results in a purer cellulosic component.
The extraction process flow of the invention is more efficient, green and environment-friendly and has high quality. (1) The microwave assisted alkali treatment replaces the ethanol Soxhlet extraction and alkali treatment process, the microwave assisted alkali treatment is used for improving the dewaxing efficiency and effect of the biomass, the conventional ethanol Soxhlet extraction process (generally 6-18 h) and the alkali treatment process (generally 10-16 h) are required to be 16-34h, the microwave assisted alkali treatment is only 0.5h, the extraction process can be shortened by more than 15h, and compared with the microwave assisted alkali treatment, the method is more rapid and efficient; (2) the low-concentration 3% hydrogen peroxide replaces the conventional 30% hydrogen peroxide or sodium hypochlorite or sodium chlorite for bleaching, so that the environmental pollution can be reduced, the corrosion and the danger of the treatment process can be reduced, and the environment is protected more; (3) the high-strength ultrasonic treatment replaces the conventional ultrasonic oscillation and high-pressure homogenization treatment, the high-strength ultrasonic treatment method is flexible, cellulose with larger size can be separated into nanometer grade through generating cavitation effect, the size is more uniform, the requirement on machine equipment is low, and the blocking condition can not be generated. The method is favorable for waste algae utilization, biomass resource development and ecological environment protection, and realizes economic sustainable development.
The cellulose nanofiber prepared by extraction has the advantages of high Young's modulus, high tensile strength, high length-diameter ratio, large specific surface area, small size effect, high reaction activity and the like, and simultaneously maintains the advantages of reproducibility, biodegradability, environmental protection, abundant sources and the like.
The cellulose nanofiber prepared by extraction of the invention has the yield of 11.4-15.1% of dry biomass, the diameter range of 10-30nm, the length of 1-10 mu m, the crystallinity index of 55-65%, the characteristic peak of cellulose I, low inorganic matter content, the ash content of only 0.7-2.6% and the thermal stability of about 345 ℃, and can be widely applied to various fields of reinforced composite materials, optical materials, medical materials, template materials, function sensor materials, food packaging and the like.
In conclusion, the preparation method disclosed by the invention has the advantages of wide sources of raw materials, low cost, simplicity and easiness in operation, high preparation efficiency, no pollution to the environment in a production process, capability of quantitative production, compliance with the concepts of green manufacturing and sustainable development, stable performance of the cellulose nanofiber prepared by extraction and wide application fields.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for preparing enteromorpha-based cellulose nanofiber based on microwave-assisted pretreatment and high-intensity ultrasound in the method of the invention.
Fig. 2 is a schematic diagram of a preparation method of enteromorpha-based cellulose nanofiber based on microwave-assisted pretreatment and high-intensity ultrasound in the method of the invention.
FIG. 3 is a schematic diagram of a microwave assisted process mechanism in the method of the present invention.
FIG. 4 is a schematic representation of the mechanism of high intensity sonication in the method of the invention.
Fig. 5 is an SEM image of the raw material enteromorpha subjected to microwave-assisted alkaline treatment, bleaching, demineralization and high-intensity ultrasonic treatment in the method of the present invention.
Fig. 6 is a TEM and particle size distribution plot of cellulose nanofibers prepared by the extraction of the present invention.
Fig. 7 is a FTIR image of cellulose nanofibers prepared by the extraction of the present invention.
Fig. 8 is an XRD pattern of cellulose nanofibers prepared by the extraction of the present invention.
FIG. 9 is a TGA-DTG plot of cellulose nanofibers prepared by the extraction of the present invention.
Fig. 10 is a diagram of a potential commercial application of the cellulose nanofibers prepared by the extraction of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it should be apparent that the described embodiments are only some of the embodiments of the present invention and should not be used to limit the protection scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Example 1: preparation of enteromorpha-based cellulose nanofiber based on microwave-assisted pretreatment and high-intensity ultrasound, the enteromorpha-based cellulose nanofiber is prepared according to the following steps:
step 1: the collected fresh enteromorpha is washed in natural seawater for several times to remove accessory organisms, put into an ice bag, brought back to a laboratory within 2 hours, washed by deionized water, dried in air at 60 ℃, crushed into fine powder by a crusher, sieved by a 100-mesh sieve and stored.
Step 2: and taking the dried enteromorpha powder, and carrying out sodium hydroxide pretreatment under microwave irradiation to induce biomass dewaxing. 50g of powdery seaweed sample is heated by microwave at 360W for 30min; naOH solution concentration 2.5M; the solid-to-liquid ratio is 1:8 (w/v); washing insoluble components with hot water for multiple times; centrifuging at 4000rpm for 15min, and freeze drying and preserving for several times until the pH of the solution is 7.
Step 3: placing dewaxed enteromorpha powder into hydrogen peroxide solution, wherein the concentration of the hydrogen peroxide is 3%, and the solid-to-liquid ratio is 1:8 (w/v); the bleaching heating temperature is 80 ℃; the time is 6.0h; after cooling to room temperature, the mixture was centrifuged at 4000rpm for 15min, the supernatant was discarded by multiple centrifugation, and the insoluble fraction was washed with water to neutral pH and stored by freeze-drying.
Step 4: suspending insoluble components in hydrochloric acid solution with concentration of 5%, dissolving freeze-dried sample in diluted hydrochloric acid with solid-to-liquid ratio of 1:5 (w/v), heating the mixture to 100deg.C for 10min, cooling to 30deg.C, maintaining at this temperature for 16h, centrifuging at 4000rpm for 10min, centrifuging for several times, and discarding supernatant; the insoluble fraction containing cellulose was washed with water several times until the pH of the solution was 7 and stored by freeze drying.
Step 5: decomposing the suspension into cellulose nanofibers by utilizing the ultrasonic action in a high-strength ultrasonic probe, and collecting and freeze-drying; preparing water suspension with the concentration of 0.5%, placing a high-strength ultrasonic probe with the frequency of 1200W and the frequency of 85%, performing ice bath environment, performing ultrasonic treatment for 1h, and freeze-drying and preserving the suspension to obtain the enteromorpha-based cellulose nanofiber.
The technical effects of the present invention will be described in detail with reference to the present experiment.
As shown in fig. 3, the microwave-assisted alkali treatment is a method of treating a natural cellulose material together with microwave radiation and an alkaline solution. In this process, the microwave functions to rapidly heat the reaction system by utilizing the characteristics of electromagnetic waves, thereby improving the reaction rate and efficiency. Specifically, microwave radiation can exacerbate the thermal motion of molecules in the reaction system, increase the impact frequency and energy between molecules, and promote the progress of chemical reaction. In addition, microwave radiation can also create electric fields and charge shifts between molecules and ions, resulting in changes in polarization and conductivity, further affecting the reaction process. In the microwave-assisted alkali treatment, the microwave has the effects of accelerating the reaction of the cellulose material and the alkaline solution, shortening the reaction time, reducing the reaction temperature and the consumption of the reactants, and realizing the efficient, energy-saving and environment-friendly reaction process.
As shown in fig. 4, the high intensity ultrasound principle is based on cavitation effects of ultrasound, i.e., mechanical and physical effects of ultrasound. The potential energy generated by the progressive expansion of the foam during cavitation is converted into kinetic energy of the liquid jet, moving through the interior of the foam and penetrating the opposite foam wall at a rate of several hundred meters per second, causing erosion damage to the fiber surface and a reduction in the cohesive forces between the fibers during collisions with the cellulose surface. The mechanical and physical effects of such ultrasonic waves can efficiently break up cellulose in a short time and obtain smaller particulate matter.
Example 2 SEM test of raw Enteromorpha prolifera in example 1 after various treatments
And observing the microscopic morphology and size of cellulose nanofiber extracted from enteromorpha by using a field emission scanning electron microscope (FES-SEM, gemini 300,Carl Zeiss AG, germany). The scanning working condition is a secondary electron mode, the experimental parameter is resolution of 4nm and accelerating voltage of 5kV.
As shown in fig. 5, SEM images of the process of preparing cellulose nanofibers by enteromorpha extraction. Wherein (a) and (b) are enteromorpha samples, (c) is a microwave-assisted alkalization sample, (d) is a bleaching sample, (e) is a demineralization sample, and (f) is a cellulose nanofiber. (c) It is shown that the excessive cutting of fibers is limited due to the high chlorophyll content in enteromorpha, while the microwave radiation is used as a substitute input energy source due to the rapid heat generation, so that the biomass structure becomes loose. (d) The bleached biomass structure is further loosened, which indicates that the binding force between the enteromorpha microfibers is reduced. This loose structure allows the acid to penetrate the fibers, making the reaction more efficient in the next acid treatment. (e) Clearly showing the fiber bundles being separated into fiber structures. As can be seen from (f), the cellulose filaments after high-intensity ultrasonic treatment are substantially separated and wound into a net-like structure.
Example 3 TEM test of Enteromorpha based cellulose nanofiber prepared in example 1
The morphology of the cellulose nanofiber is observed through TEM (JEM 2010), five-ten-million concentration cellulose nanofiber suspension is fully stirred, the ultrasonic treatment is carried out for 30min, the well-dispersed suspension is dripped on a copper mesh, the copper mesh is observed after the copper mesh is air-dried, and the accelerating voltage is 200kV.
A TEM image of enteromorpha-based cellulose nanofibers is shown in fig. 6. From the figure, the cellulose nanofiber extracted from enteromorpha is in a filament shape, and the cellulose nanofiber is inevitably entangled due to the large length-diameter ratio. Through image J software analysis, more than 200 points in the image are selected for marking, the diameter of the cellulose nanofiber is mainly distributed between 10 nm and 30nm, the cellulose nanofiber accounts for 71.22%, the cellulose nanofiber accounts for only 15.1% of the cellulose nanofiber, and the overall particle size distribution is uniform.
Example 4 Infrared Spectroscopy test of Enteromorpha based cellulose nanofiber prepared in example 1
FT-IR spectra were recorded using a Tensor 27 Fourier transform infrared spectrometer from Bruker, germany. Prior to the experiment, the samples were mixed with KBr in a mass ratio of 1/100 and pressed into transparent wafers. In each measurement, the measurement is based on 4000-400cm -1 16 cumulative scans over a range with a scan resolution of 4cm -1 。
FIG. 7 shows the IR spectrum of Enteromorpha-based cellulose nanofiber. From the figure, it can be seen that the enteromorpha-based cellulose nanofiber has typical characteristic peaks: hydroxyl telescopic vibration peak: at 3500-3200cm -1 The peak is relatively strong due to the large number of hydroxyl groups in the cellulose nanofibers. C-H stretching vibration peak: at 2850-2920cm -1 Is generated due to the high number of C-H groups contained in the cellulose nanofibers. 1636cm -1 The nearby peaks represent the water-absorbing O-H groups. 1372cm -1 And 1315cm -1 C-H bending vibration at 1429cm -1 at-CH of 2 and-OCH in-plane flexural vibration represents a cellulose group. Likewise 1162cm -1 And 1116cm -1 The nearby peaks correspond to asymmetric stretching vibrations of glycosidic linkages C-O-C and C-OH, respectively. 898cm -1 The nearby peaks are due to asymmetric stretching vibrations of the β -glycosidic bond between the anhydride glucose rings in cellulose, representing the presence of amorphous regions in cellulose.
EXAMPLE 5 XRD testing of Enteromorpha based cellulose nanofibers prepared in example 1
By X-ray diffractometer (Rigaku)Ultima IV) the crystal structure of the sample was determined and analyzed. With 40kV, 40mA Cu K alpha radiationThe sample was scanned at a speed of 6 °/min and diffraction patterns were recorded in the range of 10 ° -80 °. On the basis of the measurement records, a mathematical model describing the relationship between intensity and 2 theta is established. The crystallinity index Crl (%) of nanocellulose was then calculated according to the Segal method:
wherein I is 002 Maximum intensity of 002 lattice diffraction peak at 2θ=22.4°, I am The diffraction intensity of the amorphous portion at 2θ=18°.
An X-ray diffraction pattern of the cellulose nanofibers is shown in fig. 8. As can be seen from the figure, the sample showed 3 peaks near 2θ=16°, 22 ° and 34 °, corresponding to crystal planes (110), (002), (004), respectively, maintaining the presence of crystal domains, which are typical peaks of the cellulose i isomer, and a cellulose II type polycrystalline structure near 2θ=12°, and the appearance of no peak was found, indicating that neither chemical nor ultrasonic treatment changed the crystal structure of cellulose. According to the Segal method, the crystallinity index Crl (%) of the enteromorpha-based cellulose nanofiber is 63.1%.
Example 5 thermogravimetric analysis test of Enteromorpha-based cellulose nanofiber prepared in example 1
The thermal stability of the samples at 50mL/min nitrogen flow was determined using a thermogravimetric analyzer (TA, TGA 55). The test conditions are that the temperature rising rate is 10 ℃/min, the temperature scanning range is 30-800 ℃, and the temperature is controlled by O 2 Instead of N 2 Preserving heat at 800 ℃ for 15min. The flow rate was set at 50mL/min. Coke content was calculated as sample N 2 The ash content was calculated as the mass remaining after the end of the heating procedure. FIG. 9 shows the thermogravimetric analysis of Enteromorpha-based cellulose nanofiber (TGA and DTG curves). When the temperature reaches 100 ℃, the absorbed water evaporatesThe mass of the cellulose component was reduced by 5% (w/w). As observed in the infrared spectroscopy study, at 1636cm -1 The presence of absorbed water was also detected, indicating hydrogen bonding between water molecules. In the high temperature range, the enteromorpha-based cellulose nanofiber has a main pyrolysis process and mainly loses weight in the range of 251.4-372.3 ℃. The initial thermal decomposition temperature of the enteromorpha-based cellulose nanofiber occurs at 269 ℃, the maximum thermal decomposition temperature is 345 ℃, and ash content is 1.8% (w/w), which indicates that the stability is high and most of inorganic impurities are removed.
As shown in figure 10, the enteromorpha-based cellulose nanofiber has high Young's modulus, high tensile strength, high length-diameter ratio, large specific surface area, small size effect and high reactivity, maintains the benefit of renewable, biodegradable, environment-friendly and abundant-source natural cellulose, has very broad commercial application prospect, and is widely applied to the fields of concrete, reinforced composite materials, papermaking products, packaging products, cosmetics, food additives, coatings/coatings, biomedical materials and the like.
While the invention has been described with reference to the above embodiments, it will be understood that the invention is capable of further modifications and variations without departing from the spirit of the invention, and these modifications and variations are within the scope of the invention.
Claims (9)
1. The preparation method of the enteromorpha-based cellulose nanofiber is characterized by comprising the following steps of:
step 1: washing the collected fresh enteromorpha in natural seawater for several times, preserving at low temperature, repeatedly washing with water to remove precipitate impurities, drying, and pulverizing into enteromorpha powder;
step 2: taking enteromorpha powder, pretreating with sodium hydroxide under microwave irradiation, and inducing biomass dewaxing, wherein the specific operation steps are as follows: under the microwave irradiation of 360W, the enteromorpha powder is heated by microwaves, and simultaneously NaOH solution is added for pretreatment to induce the dewaxing of biomass; the solid-to-liquid ratio of the enteromorpha powder to the NaOH solution is 1:5-1:10 (w/v), the concentration of the NaOH solution is 1.0-3.0M, and the time is 20-90min; washing insoluble components with hot water for multiple times, centrifuging for multiple times until the pH of the solution is neutral, and freeze-drying and preserving;
step 3: placing dewaxed enteromorpha powder into hydrogen peroxide solution, heating and bleaching, removing pigment, centrifugally washing with distilled water until the solution is neutral, and drying;
step 4: suspending insoluble components in hydrochloric acid solution, heating to boiling, cooling, stirring the solution, centrifuging to remove supernatant, and washing with deionized water for multiple times until the solution is neutral;
step 5: the suspension is decomposed into cellulose nanofibers by ultrasonic action in a high-strength ultrasonic probe, and the cellulose nanofibers are collected and freeze-dried.
2. The method for preparing enteromorpha-based cellulose nanofiber as set forth in claim 1, wherein:
the drying in the step 1 is carried out by placing the enteromorpha into a blast drying oven for air drying at 60 ℃, the crushing in the step 1 is carried out by crushing enteromorpha into fine powder by using a crusher, and sieving the fine powder by 100 meshes.
3. The method for preparing enteromorpha-based cellulose nanofiber according to claim 1, wherein the specific operation steps of the step 3 are as follows: placing dewaxed Enteromorpha prolifera powder into H with concentration of 3% 2 O 2 In the solution, enteromorpha powder and H 2 O 2 The solid-liquid ratio of the solution is 1:6-1:12 (w/v); heating and bleaching at 70-90 ℃ for 5.5-10h; after cooling to room temperature, centrifuging for 10-20min, centrifuging for several times, discarding supernatant, washing insoluble components with water to neutral pH, and freeze drying for preservation.
4. The method for preparing enteromorpha-based cellulose nanofiber according to claim 1, wherein the specific operation steps of the step 4 are as follows: suspending insoluble components in 3-8% HCl solution, heating to 100deg.C for 5-15min; cooling to 30deg.C, maintaining at the temperature for 14-24 hr, centrifuging for 10min, centrifuging for several times, and removing supernatant; the insoluble components were washed with water several times until the pH of the solution was neutral, and stored by freeze drying.
5. The method for preparing enteromorpha-based cellulose nanofiber according to claim 1, wherein the specific operation steps of step 5 are as follows: dissolving a freeze-dried sample in water, preparing water suspension with the concentration of 0.2-1%, placing the suspension into a high-intensity ultrasonic probe with the probe frequency of 1200W, the probe frequency of 70-95%, an ice bath environment and the ultrasonic time of 0.5-2h, and freeze-drying and preserving the suspension to obtain the enteromorpha cellulose nanofiber.
6. An enteromorpha-based cellulose nanofiber, characterized in that: is prepared by the preparation method of the enteromorpha-based cellulose nanofiber according to any one of claims 1 to 5.
7. The enteromorpha-based cellulose nanofiber as set forth in claim 6, wherein: the enteromorpha-based cellulose nanofiber has the diameter range of 10-30nm, the length of 1-10 mu m, the length-diameter ratio of 120-310, the filament shape, the crystallinity index of 55-65% and the water retention rate of 7.02-7.85; the enteromorpha-based cellulose nanofiber shows a characteristic peak of typical cellulose I; the main degradation interval of the enteromorpha-based cellulose nanofiber is 251.4-372.3 ℃, the maximum thermal degradation temperature is 345 ℃, the inorganic matter content is low, and the ash content is only 0.7-2.6%.
8. The enteromorpha-based cellulose nanofiber according to claim 7, characterized in that: the yield of the enteromorpha-based cellulose nanofiber is 11.4-15.1% of the dry biomass.
9. The use of the enteromorpha-based cellulose nanofiber prepared by the preparation method of the enteromorpha-based cellulose nanofiber according to any one of claims 1 to 5 in the preparation of reinforced composite materials, paper products, cosmetics, paints and biomedical materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310670135.8A CN116446213B (en) | 2023-06-07 | 2023-06-07 | Enteromorpha-based cellulose nanofiber, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310670135.8A CN116446213B (en) | 2023-06-07 | 2023-06-07 | Enteromorpha-based cellulose nanofiber, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116446213A CN116446213A (en) | 2023-07-18 |
| CN116446213B true CN116446213B (en) | 2023-12-22 |
Family
ID=87132293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310670135.8A Active CN116446213B (en) | 2023-06-07 | 2023-06-07 | Enteromorpha-based cellulose nanofiber, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116446213B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431231A (en) * | 2003-01-29 | 2003-07-23 | 广西壮族自治区中国科学院广西植物研究所 | Method for extracting xylan from woody fiber material |
| CN103190656A (en) * | 2013-04-17 | 2013-07-10 | 桂林理工大学 | Method for obtaining effective substances from enteromorpha |
| CN103255662A (en) * | 2013-05-06 | 2013-08-21 | 青岛大学 | Preparation method of nanometer fibril enteromorpha cellulose |
| CN104098715A (en) * | 2014-07-16 | 2014-10-15 | 中国科学院海洋研究所 | Method for degrading chitosan through microwave-enzyme method coupling |
| CN107345372A (en) * | 2016-05-05 | 2017-11-14 | 中国农业科学院农业环境与可持续发展研究所 | It is a kind of that cellulose nano-fibrous method is prepared based on biomass material |
| CN111893789A (en) * | 2020-07-28 | 2020-11-06 | 山东科技大学 | Preparation method and application of nano fibrillated cellulose |
-
2023
- 2023-06-07 CN CN202310670135.8A patent/CN116446213B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431231A (en) * | 2003-01-29 | 2003-07-23 | 广西壮族自治区中国科学院广西植物研究所 | Method for extracting xylan from woody fiber material |
| CN103190656A (en) * | 2013-04-17 | 2013-07-10 | 桂林理工大学 | Method for obtaining effective substances from enteromorpha |
| CN103255662A (en) * | 2013-05-06 | 2013-08-21 | 青岛大学 | Preparation method of nanometer fibril enteromorpha cellulose |
| CN104098715A (en) * | 2014-07-16 | 2014-10-15 | 中国科学院海洋研究所 | Method for degrading chitosan through microwave-enzyme method coupling |
| CN107345372A (en) * | 2016-05-05 | 2017-11-14 | 中国农业科学院农业环境与可持续发展研究所 | It is a kind of that cellulose nano-fibrous method is prepared based on biomass material |
| CN111893789A (en) * | 2020-07-28 | 2020-11-06 | 山东科技大学 | Preparation method and application of nano fibrillated cellulose |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116446213A (en) | 2023-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nang An et al. | Extraction of high crystalline nanocellulose from biorenewable sources of Vietnamese agricultural wastes | |
| Hu et al. | Preparation of cellulose nanocrystals and carboxylated cellulose nanocrystals from borer powder of bamboo | |
| Wang et al. | Isolation and characterization of cellulose nanocrystals from pueraria root residue | |
| Wang et al. | Reuse of waste cotton cloth for the extraction of cellulose nanocrystals | |
| Kallel et al. | Isolation and structural characterization of cellulose nanocrystals extracted from garlic straw residues | |
| Feng et al. | Extraction and preparation of cellulose nanocrystals from dealginate kelp residue: structures and morphological characterization | |
| Li et al. | Cellulose whiskers extracted from mulberry: A novel biomass production | |
| CN105568730A (en) | Method for preparing renewable nano-celluloses | |
| Du et al. | A co-production of sugars, lignosulfonates, cellulose, and cellulose nanocrystals from ball-milled woods | |
| Song et al. | Utilization of deep eutectic solvent as a degumming protocol for Apocynum venetum bast | |
| Fan et al. | Comparative study on enhanced pectinase and alkali-oxygen degummings of sisal fibers | |
| Nehra et al. | Facile synthesis of nanocellulose from wheat straw as an agricultural waste | |
| CN105017541A (en) | Banana cellulose crystallite/polylactic acid aerogel and preparation method and use thereof | |
| Yang et al. | Isolating cellulose nanofibers from steam-explosion pretreated corncobs using mild mechanochemical treatments | |
| Wu et al. | Production of cellulose nanofibrils and films from elephant grass using deep eutectic solvents and a solid acid catalyst | |
| Zhang et al. | Preparation and characterization of cellulose nanofibers isolated from lettuce peel | |
| Abdullah et al. | Structure and thermal properties of microcrystalline cellulose extracted from coconut husk fiber | |
| Rao et al. | Extraction and characterization of cellulose from agricultural waste materials | |
| Zhao et al. | Allomorphic regulation of bamboo cellulose by mild alkaline peroxide for holocellulose nanofibrils production | |
| CN116446213B (en) | Enteromorpha-based cellulose nanofiber, preparation method and application | |
| Yao et al. | Structural and optical properties of cellulose nanocrystals isolated from the fruit shell of Camellia oleifera Abel | |
| Hernández Pérez et al. | Comparing Acid and Enzymatic Hydrolysis Methods for Cellulose Nanocrystals (CNCs) Obtention from Agroindustrial Rice Husk Waste | |
| Karunakaran et al. | Extraction of micro, nanocrystalline cellulose and textile fibers from coffee waste | |
| Petrik et al. | Isolation and characterisation of cellulose nanocrystal obtained from sugarcane peel | |
| CN111893789A (en) | Preparation method and application of nano fibrillated cellulose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |