CN104047198A - Preparation method for nano-cellulose - Google Patents
Preparation method for nano-cellulose Download PDFInfo
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- CN104047198A CN104047198A CN201310081960.0A CN201310081960A CN104047198A CN 104047198 A CN104047198 A CN 104047198A CN 201310081960 A CN201310081960 A CN 201310081960A CN 104047198 A CN104047198 A CN 104047198A
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Abstract
The invention relates to a preparation method for nano-cellulose. The method comprises the steps of: providing a plant fiber pulp; untwining the plant fiber pulp to separate the plant fiber into single fiber; conducting pre-defiberization treatment on the untwined plant fiber pulp, and simultaneously adding a TEMPO catalytic oxidation system to oxidize the fiber; when the freeness of the plant fiber pulp reaches 150-450ml, separating the oxidized fiber and wastewater; conducting defiberization treatment on the oxidized fiber again to freeness of 50ml and below, thus obtaining defiberized oxidized fiber; and carrying out nanocrystallization treatment on the defiberized oxidized fiber so as to obtain a nano-cellulose solution. The method is easier to realize wastewater separation and recovery of chemicals, at the same time can save pulping energy consumption by 20%-82%, and is easier to obtain nano-cellulose with uniform size and low cost.
Description
Technical field
The present invention relates to a kind of method of preparing nano-cellulose.
Background technology
Nano-cellulose fiber refers to that cross section is the fiber of nano-scale, and its cross-sectional diameter is generally less than 100nm.Nano-cellulose has larger specific area and higher mechanical strength properties, has the character different from natural plant fibre, can be used as pharmaceutical carrier, dispersant, membrane material and nano composite material reinforcing agent etc.At present nano-cellulose mainly comprises nano cellulose crystal (NCC) prepared by chemical method (mineral acid hydrolysis), or the nanometer fibrillation cellulose (NFC) prepared of Mechanical Method.Adopt inorganic acid (hydrochloric acid, sulfuric acid) prepare the method yield very low (being about 30%) of NCC and need to consume a large amount of acid, cause that production cost is high, power consumption is large, contaminated environment etc.And the nano-cellulose fiber size heterogeneity that adopts Mechanical Method to prepare by the equipment such as microfluidization device or high pressure homogenizer, still there is more micron order structure in size, simultaneously owing to adopting mechanical method to separate microfibril, fiber need to be processed the fiber that could obtain reduced size for tens of times through high pressure homogenizer or microfluidization device, need to consume a large amount of energy, production cost is high.
Adopt at present TEMPO oxidizing process to prepare nano-cellulose, need carry out defibrination/making beating to string and separate fine processing to the freedom of slurry and reach below 100ml, and then add TEMPO oxidation system processing slurry.Separate fine processing and can improve the accessibility of chemicals to fiber, accelerate reaction efficiency.But the method has consumed a large amount of energy in the process of plant fiber material defibrination/making beating; After the slurry of low freedom carries out TEMPO oxidation on the other hand, water separation capability worsens, and is unfavorable for the separation of oxidized waste water and the recovery of chemicals.
Summary of the invention
In view of this, be necessary to provide a kind of method of preparing nano-cellulose, the method energy consumption is low and be conducive to separate waste water and chemicals.
A method of preparing nano-cellulose, it comprises the steps:
Vegetable-fibre slurry is provided;
Vegetable-fibre slurry is discongested and made string be separated into single fiber;
Vegetable-fibre slurry after discongesting is carried out to pre-fine processing of separating, separate in advance fine time and add TEMPO catalytic oxidation system to be oxidized fiber;
In the time that vegetable-fibre slurry freedom reaches 150-450ml, the fiber after separation of oxygenated and waste water;
Fiber after oxidation is separated to fibre again to be processed to freedom and reaches 50ml and the following oxidized fibre that obtains separating after fibre;
The oxidized fibre of separating after fibre is carried out to nanometer processing, obtain nanofiber cellulose solution.
The present invention, fiber is carried out to completed in the fine process of pre-solution the TEMPO oxidation of slurry simultaneously, utilizes the accessibility that in fine process, the effect of peeling off of fiber finer cell wall has been improved TEMPO oxidation system separating, and has improved the efficiency of oxidation reaction; The carboxyl producing in simultaneous oxidation course of reaction has promoted again the swollen of fiber conversely, has promoted the dissociation process of fiber.In addition due in the time that freedom is higher to the oxidation slurry separation of dewatering, while having avoided slurry freedom very low, the separation difficulty of oxidation slurry and oxidized waste water, is easy to the recovery of medicine.The method more easily realizes that waste water separates and chemicals recovery time, can save beating energy consumption 20%-82%, and more easily obtains size homogeneous, nano-cellulose with low cost.
Detailed description of the invention
A method of preparing nano-cellulose, it comprises the steps:
(1) provide vegetable-fibre slurry.This string is at least one in softwood, broadleaf, grass family raw material, is preferably softwood or broadleaf fiber.
(2) vegetable-fibre slurry is discongested and made string be separated into single fiber uniformly.This step can adopt fluffer or hydrabrusher to discongest vegetable-fibre slurry, and the time of discongesting is preferably 10-30min.
(3) vegetable-fibre slurry after discongesting is carried out to pre-separate fine process (processing of making beating/defibrination), separate in advance fine time and add TEMPO catalytic oxidation system to be oxidized fiber.This TEMPO catalytic oxidation system comprises TEMPO, cocatalyst and oxidant, and wherein TEMPO is 2,2,6,6-tetramethyl-1-piperidines-N-oxygen radical and derivative thereof.Cocatalyst is one or more in metal bromide, metal iodide, metal perborate salt compound, as sodium bromide (NaBr).Oxidant is clorox (NaClO).The addition of TEMPO is the 0.01%-1% of vegetable-fibre slurry over dry quality, and the addition of cocatalyst is that the 0.1%-10% of vegetable-fibre slurry over dry quality, the addition of oxidant are the 1.5%-150% of vegetable-fibre slurry over dry quality.The equipment of separating fine processing use can be trough-style pulp beater, PFI grinds (beating machine or vertical beating machine), the dense single-deck of middle height or double disc refiner.While adding TEMPO catalytic oxidation system, the pH value of this slurry system preferably remains 10-10.5.The adjusting of pH can adopt hydrochloric acid solution and sodium hydroxide solution.
Separate the accessibility that in fine process, the effect of peeling off of fiber finer cell wall has been improved TEMPO oxidation system, improved the efficiency of oxidation reaction; The carboxyl producing in simultaneous oxidation course of reaction has promoted again the swollen of fiber conversely, has promoted the dissociation process of fiber.
(4) be preferably 200-400ml when vegetable-fibre slurry freedom reaches 150-450ml() time, fiber and oxidized waste water after filter plant separation of oxygenated utilized; And the oxidized fibre after separating is washed.Washing times is preferably 3-5 time.
In the time that freedom is higher, to the oxidation slurry separation of dewatering, while having avoided slurry freedom very low, the separation difficulty of oxidation slurry and oxidized waste water, is easy to the recovery of medicine.
(5) oxidized fibre after washing is inserted again separate and separate fibre in fine equipment and process to freedom and reach 50ml and following, obtain separating the oxidized fibre after fibre.
(6) by separating oxidized fibre after fibre and be diluted to the concentration of 0.1%-10%, utilize nanometer equipment to carry out nanometer processing, obtain the nanofiber cellulose solution of transparent homogeneous.This nanometer equipment can be high pressure homogenizer, microfluidization device or processor for ultrasonic wave.
The carboxyl-content of the nano-cellulose that the method makes is 0.2-1.5mmol/g, and size homogeneous, stable storage.
The present invention, fiber is carried out to completed in the fine process of pre-solution the TEMPO oxidation of slurry simultaneously, utilizes the accessibility that in fine process, the effect of peeling off of fiber finer cell wall has been improved TEMPO oxidation system separating, and has improved the efficiency of oxidation reaction; The carboxyl producing in simultaneous oxidation course of reaction has promoted again the swollen of fiber conversely, has promoted the dissociation process of fiber.In addition due in the time that freedom is higher to the oxidation slurry separation of dewatering, while having avoided slurry freedom very low, the separation difficulty of oxidation slurry and oxidized waste water, is easy to the recovery of medicine.The method more easily realizes that waste water separates and chemicals recovery time, can save beating energy consumption 20%-82%, and more easily obtains size homogeneous, nano-cellulose with low cost.
Below by specific embodiment, the present invention is described further.
Comparative example
Get 360g softwood Pulp Fibers (oven dry stock) and be placed in trough-style pulp beater, discongest after 30min, apply 2kg stone roller and pull an oar.Separating fine 240min disposed slurry freedom is 300ml, pull an oar subsequently to freedom be 50ml.Freedom is that the slurry of 50ml utilizes high pressure homogenizer nanometer processing 35pass under 90MPa to obtain the nanofiber cellulose solution of transparent and homogeneous.
Note: adding top is the operation for beater, the object that adds top is that under certain pressure, fiber is cut off or wire-dividing broom purification in order to apply certain beating pressure.Cellulose need to be through repeatedly just obtaining nano-cellulose after circular treatment, and institute's processing sample is all once 1pass through high-pressure homogeneous processing.
Embodiment 1
Get 360g softwood Pulp Fibers (oven dry stock) and be placed in trough-style pulp beater, discongest after 30min, add the TEMPO of 2g, the NaBr of 24g, (mass percentage concentration is 10% to the NaClO solution of 60ml, approximately containing 6.6g over dry NaClO), apply 2kg stone roller and pull an oar, 190min disposed slurry freedom separates oxidized fibre and waste water while being 295ml.Wash oxidized fibre after 4 times continue to pull an oar to freedom be 50ml, the carboxyl-content of the oxidized fibre obtaining is 0.21mmol/g, oxidized fibre utilizes high pressure homogenizer nanometer under 90MPa to process 28pass to obtain the nanofiber cellulose solution of transparent and homogeneous.
Compared with comparative example, the fine preliminary treatment Energy Intensity Reduction 20.8% of the present embodiment solution, nanometer is processed and is saved energy consumption 20%.
Note: because embodiment uses identical beating equipment and nanometer equipment with comparative example, same plant capacity, therefore in embodiment and comparative example, making beating is separated the height of fine energy consumption to the time length explanation of identical freedom cost, and the nanofiber cellulose solution that nanometer obtains transparent and homogeneous spends the height of how many explanation nanometer energy consumptions of pass number.
Embodiment 2
Get 360g softwood Pulp Fibers (oven dry stock) and be placed in trough-style pulp beater, discongest after 30min, add the TEMPO of 2g, the NaBr of 24g, (mass percentage concentration is 10% to the NaClO solution of 1250ml, approximately containing 137.5g over dry NaClO), apply 2kg stone roller and pull an oar, 120min disposed slurry freedom separates oxidized fibre and waste water while being 305ml.Wash oxidized fibre after 4 times continue to pull an oar to freedom be 50ml, the carboxyl-content of the oxidized fibre obtaining is 0.82mmol/g, oxidized fibre utilizes high pressure homogenizer nanometer under 90MPa to process 12pass to obtain the nanofiber cellulose solution of transparent and homogeneous.
Compared with comparative example, the fine preliminary treatment Energy Intensity Reduction 50% of the present embodiment solution, nanometer is processed and is saved energy consumption 85.7%.
Embodiment 3
Get 360g softwood Pulp Fibers (oven dry stock) and be placed in trough-style pulp beater, discongest after 30min, add the TEMPO of 2g, the NaBr of 24g, (mass percentage concentration is 10% to the NaClO solution of 2500ml, approximately containing 275g over dry NaClO), apply 2kg stone roller and pull an oar, 45min disposed slurry freedom separates oxidized fibre and waste water while being 240ml.Wash oxidized fibre after 4 times continue to pull an oar to freedom be 50ml, the oxidized fibre carboxyl-content obtaining is 1.45mmol/g, oxidized fibre utilizes high pressure homogenizer nanometer under 90MPa to process 3pass to obtain the nanofiber cellulose solution of transparent and homogeneous.
Compared with comparative example, the fine preliminary treatment Energy Intensity Reduction 81.3% of the present embodiment solution, nanometer is processed and is saved energy consumption 91.4%.
In addition, those skilled in the art also can make various amendments, interpolation and the replacement in other form and details in the claims in the present invention scope of disclosure and spirit.Certainly, the variations such as various amendments, interpolation and the replacement that these make according to spirit of the present invention, within all should being included in the present invention's scope required for protection.
Claims (11)
1. a method of preparing nano-cellulose, it comprises the steps:
Vegetable-fibre slurry is provided;
Vegetable-fibre slurry is discongested and made string be separated into single fiber;
Vegetable-fibre slurry after discongesting is carried out to pre-fine processing of separating, separate in advance fine time and add TEMPO catalytic oxidation system to be oxidized fiber;
In the time that vegetable-fibre slurry freedom reaches 150-450ml, the fiber after separation of oxygenated and waste water;
Fiber after oxidation is separated to fibre again to be processed to freedom and reaches 50ml and the following oxidized fibre that obtains separating after fibre;
The oxidized fibre of separating after fibre is carried out to nanometer processing, obtain nanofiber cellulose solution.
2. the method for preparing nano-cellulose as claimed in claim 1, is characterized in that: this string is at least one in softwood, broadleaf, grass family raw material.
3. the method for preparing nano-cellulose as claimed in claim 1, is characterized in that: the equipment that the step that vegetable-fibre slurry is discongested adopts is fluffer or hydrabrusher.
4. the method for preparing nano-cellulose as claimed in claim 1, is characterized in that: the time of discongesting of the step that vegetable-fibre slurry is discongested is 10-30min.
5. the method for preparing nano-cellulose as claimed in claim 1, it is characterized in that: this TEMPO catalytic oxidation system comprises TEMPO, cocatalyst and oxidant, wherein TEMPO is 2,2,6,6-tetramethyl-1-piperidines-N-oxygen radical and derivative thereof, the addition of TEMPO is the 0.01%-1% of vegetable-fibre slurry over dry quality; Cocatalyst is one or more in metal bromide, metal iodide, metal perborate salt compound, and cocatalyst addition is the 0.1%-10% of vegetable-fibre slurry over dry quality; Oxidant is clorox, and the addition of oxidant is the 1.5%-150% of vegetable-fibre slurry over dry quality.
6. the method for preparing nano-cellulose as claimed in claim 1, is characterized in that: separating the fine equipment using of processing is trough-style pulp beater, PFI mill, the dense single-deck of middle height or double disc refiner.
7. the method for preparing nano-cellulose as claimed in claim 1, is characterized in that: while adding TEMPO catalytic oxidation system, the pH value of this slurry system is 10-10.5.
8. the method for preparing nano-cellulose as claimed in claim 1, is characterized in that: when vegetable-fibre slurry freedom reaches 200-400ml, and the fiber after separation of oxygenated and waste water.
9. the method for preparing nano-cellulose as claimed in claim 1, is characterized in that: after fiber and waste water after separation of oxygenated, need wash and separate fine processing again the fiber after oxidation.
10. the method for preparing nano-cellulose as claimed in claim 1, is characterized in that: the step of nanometer processing needs first the oxidized fibre after solution fibre to be diluted to the concentration of 0.1%-10%.
11. methods of preparing nano-cellulose as claimed in claim 1, is characterized in that: the equipment that the step of nanometer processing is used is high pressure homogenizer, microfluidization device or processor for ultrasonic wave.
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Cited By (13)
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| CN104389240A (en) * | 2014-10-17 | 2015-03-04 | 广西大学 | Preparation method of nanometer antibacterial agent for paper |
| CN105199004A (en) * | 2015-09-10 | 2015-12-30 | 华南理工大学 | Method for producing NFC (nano-fibrillated cellulose) |
| CN105329863A (en) * | 2015-08-11 | 2016-02-17 | 中国制浆造纸研究院 | Method for recovering oxynitrides from nanometer cellulose preparation waste liquid |
| CN105369663A (en) * | 2015-08-11 | 2016-03-02 | 中国制浆造纸研究院 | High-efficiency and low-energy-loss nanocellulose preparation method |
| CN105568728A (en) * | 2015-12-03 | 2016-05-11 | 雷春生 | Method for preparing nanocellulose from Urtica fissa stalks |
| CN105566502A (en) * | 2015-12-21 | 2016-05-11 | 同济大学 | Preparation method of waterproof renewable nano cellulose thin film |
| CN106268679A (en) * | 2016-09-22 | 2017-01-04 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of chitosan nano fiber element base composite spherical adsorbing material |
| CN106423077A (en) * | 2016-09-22 | 2017-02-22 | 东莞市联洲知识产权运营管理有限公司 | Modified nano-crystalline cellulose and preparing method and application of fiber thereof |
| CN108049230A (en) * | 2017-12-14 | 2018-05-18 | 天津科技大学 | A kind of iron catalyzing hydrogen peroxide oxidation prepares nano-cellulose method |
| CN109153732A (en) * | 2016-05-25 | 2019-01-04 | 赛佩荷兰服务有限公司 | The production of the nano-cellulose of chemical derivatization |
| TWI741792B (en) * | 2020-09-16 | 2021-10-01 | 臺灣塑膠工業股份有限公司 | Use of prebiotic cellulose nanofiber of preparing composition for improving probiotic activities |
| CN113774711A (en) * | 2021-10-07 | 2021-12-10 | 华南理工大学 | Pineapple whole-leaf antibacterial powder coating and preparation method thereof |
| CN116623458A (en) * | 2023-07-11 | 2023-08-22 | 浙江科技学院 | Preparation method of lignocellulose |
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Cited By (19)
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| CN104389240A (en) * | 2014-10-17 | 2015-03-04 | 广西大学 | Preparation method of nanometer antibacterial agent for paper |
| CN105329863A (en) * | 2015-08-11 | 2016-02-17 | 中国制浆造纸研究院 | Method for recovering oxynitrides from nanometer cellulose preparation waste liquid |
| CN105369663A (en) * | 2015-08-11 | 2016-03-02 | 中国制浆造纸研究院 | High-efficiency and low-energy-loss nanocellulose preparation method |
| CN105369663B (en) * | 2015-08-11 | 2018-09-07 | 中国制浆造纸研究院 | A kind of method that high efficiency, low energy consumption prepare nano-cellulose |
| CN105199004B (en) * | 2015-09-10 | 2018-01-16 | 华南理工大学 | A kind of cellulose that produces receives the method for silk |
| CN105199004A (en) * | 2015-09-10 | 2015-12-30 | 华南理工大学 | Method for producing NFC (nano-fibrillated cellulose) |
| CN105568728A (en) * | 2015-12-03 | 2016-05-11 | 雷春生 | Method for preparing nanocellulose from Urtica fissa stalks |
| CN105566502B (en) * | 2015-12-21 | 2018-06-26 | 同济大学 | The preparation method of the renewable nano-cellulose film of water resistance |
| CN105566502A (en) * | 2015-12-21 | 2016-05-11 | 同济大学 | Preparation method of waterproof renewable nano cellulose thin film |
| CN109153732A (en) * | 2016-05-25 | 2019-01-04 | 赛佩荷兰服务有限公司 | The production of the nano-cellulose of chemical derivatization |
| CN109153732B (en) * | 2016-05-25 | 2021-02-19 | 赛佩荷兰服务有限公司 | Production of chemically derivatized nanocellulose |
| US11485797B2 (en) | 2016-05-25 | 2022-11-01 | Sappi Netherlands Services B.V. | Production of chemically derivatized nanocellulose |
| CN106423077A (en) * | 2016-09-22 | 2017-02-22 | 东莞市联洲知识产权运营管理有限公司 | Modified nano-crystalline cellulose and preparing method and application of fiber thereof |
| CN106268679A (en) * | 2016-09-22 | 2017-01-04 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of chitosan nano fiber element base composite spherical adsorbing material |
| CN106268679B (en) * | 2016-09-22 | 2019-06-18 | 海安县中山合成纤维有限公司 | A kind of preparation method of chitosan nano fiber element base composite spherical adsorbent material |
| CN108049230A (en) * | 2017-12-14 | 2018-05-18 | 天津科技大学 | A kind of iron catalyzing hydrogen peroxide oxidation prepares nano-cellulose method |
| TWI741792B (en) * | 2020-09-16 | 2021-10-01 | 臺灣塑膠工業股份有限公司 | Use of prebiotic cellulose nanofiber of preparing composition for improving probiotic activities |
| CN113774711A (en) * | 2021-10-07 | 2021-12-10 | 华南理工大学 | Pineapple whole-leaf antibacterial powder coating and preparation method thereof |
| CN116623458A (en) * | 2023-07-11 | 2023-08-22 | 浙江科技学院 | Preparation method of lignocellulose |
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