CN104047198B - The method preparing nano-cellulose - Google Patents
The method preparing nano-cellulose Download PDFInfo
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- CN104047198B CN104047198B CN201310081960.0A CN201310081960A CN104047198B CN 104047198 B CN104047198 B CN 104047198B CN 201310081960 A CN201310081960 A CN 201310081960A CN 104047198 B CN104047198 B CN 104047198B
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Abstract
A kind of method preparing nano-cellulose, it comprises the steps: to provide vegetable-fibre slurry；Vegetable-fibre slurry is discongested and makes Plant fiber be separated into single fiber；Vegetable-fibre slurry after discongesting carries out the pre-fibre that solves process, add TEMPO catalytic oxidation system while pre-solution fibre and fiber is aoxidized；When vegetable-fibre slurry freedom reaches 150 450ml, separate the fiber after oxidation and waste water；Fiber after oxidation is solved again fine process to freedom and reaches 50ml and the following oxidized fibre obtained after solving fibre；Oxidized fibre after solving fibre is carried out nanorize process, obtains nanofiber cellulose solution.The method is easier to realize waste water and separates and while chemical drugs reclaims, and can save beating energy consumption 20% 82%, and be easier to obtain size uniformity, nano-cellulose with low cost.
Description
Technical field
The present invention relates to a kind of method preparing nano-cellulose.
Background technology
Nano-cellulose fiber refers to the fiber that cross section is nano-scale, its cross-sectional diameter
It is generally less than 100nm.Nano-cellulose has bigger specific surface area and higher machinery is strong
Degree performance, there is the character different from natural plant fibre, can as pharmaceutical carrier, point
Powder, membrane material and nano composite material reinforcing agent etc..Nano-cellulose mainly includes at present
Nano cellulose crystal (NCC) prepared by chemical method (mineral acid hydrolysis), or Mechanical Method
Nanometer fibrillation cellulose (NFC) of preparation.Mineral acid (hydrochloric acid, sulphuric acid) is used to prepare
The method yield the lowest (about 30%) of NCC and need to consume substantial amounts of acid, causes production
Cost is high, power consumption is big, pollute environment etc..And set by microfluidization device or high pressure homogenizer etc.
The standby nano-cellulose fiber size heterogeneity using Mechanical Method to prepare, size still suffers from more
Micron scale construction, simultaneously because use machinery method separation microfibril, fiber need through
High pressure homogenizer or microfluidization device process the fiber that could obtain reduced size tens of times, need
Consuming substantial amounts of energy, production cost is high.
Use TEMPO oxidizing process to prepare nano-cellulose at present, Plant fiber need to be carried out
The freedom of defibrination/making beating solution fibre process to slurry reaches below 100ml, then adds
TEMPO oxidation system processes slurry.Solve fibre process can improve chemical drugs to fiber can and
Degree, accelerates reaction efficiency.But, the method is in the process of plant fiber material defibrination/making beating
In consume substantial amounts of energy；The slurry of the lowest freedom carries out TEMPO oxidation
Rear water separation capability deteriorates, and is unfavorable for the separation of oxidized waste water and the recovery of chemical drugs.
Summary of the invention
In view of this, it is necessary to a kind of method preparing nano-cellulose, the method energy are provided
Consume low and be conducive to separating waste water and chemical drugs.
A kind of method preparing nano-cellulose, it comprises the steps:
Vegetable-fibre slurry is provided；
Vegetable-fibre slurry is discongested and makes Plant fiber be separated into single fiber；
Vegetable-fibre slurry after discongesting carries out the pre-fibre that solves process, add while pre-solution fibre
Fiber is aoxidized by TEMPO catalytic oxidation system；
When vegetable-fibre slurry freedom reaches 150-450ml, separate the fiber after oxidation
And waste water；
Fiber after oxidation is solved again fine process to freedom and reaches 50ml and following
Obtain the oxidized fibre after solving fibre；
Oxidized fibre after solving fibre is carried out nanorize process, obtains nanofiber cellulose solution.
The present invention completes slurry during fiber carries out pre-solution fibre simultaneously
TEMPO aoxidizes, and utilizes and improves the release effect of fiber finer cell wall during solving fibre
The accessibility of TEMPO oxidation system, improves the efficiency of oxidation reaction；Simultaneous oxidation is reacted
During the carboxyl that produces promote the swollen of fiber the most in turn, promote dissociating of fiber
Process.Separate additionally, due to oxidation slurry being carried out when freedom is higher dehydration, it is to avoid
The separation difficulty of oxidation slurry and oxidized waste water when stock freeness is the lowest, it is easy to returning of medicine
Receive.The method is easier to realize waste water and separates and while chemical drugs recovery, can save and beat
Slurry energy consumption 20%-82%, and be easier to obtain size uniformity, nano-cellulose with low cost.
Detailed description of the invention
A kind of method preparing nano-cellulose, it comprises the steps:
(1) vegetable-fibre slurry is provided.This Plant fiber is softwood, broadleaf, standing grain basis
At least one in section's raw material, preferably softwood or broadleaf fiber.
(2) vegetable-fibre slurry is discongested that to make Plant fiber be separated into the most single
Fiber.This step can use fluffer or hydrabrusher to discongest vegetable-fibre slurry,
The time of discongesting is preferably 10-30min.
(3) vegetable-fibre slurry after discongesting carries out the pre-fibre that solves to process (at making beating/defibrination
Reason), add TEMPO catalytic oxidation system while pre-solution fibre and fiber is aoxidized.Should
TEMPO catalytic oxidation system includes TEMPO, cocatalyst and oxidant, wherein
TEMPO is 2,2,6,6-tetramethyl-1-piperidines-N-oxygen-derived free radicals and derivant thereof.Auxiliary is urged
Agent is the one in metal bromide, metal iodide, metal borate compound or many
Kind, such as sodium bromide (NaBr).Oxidant is sodium hypochlorite (NaClO).TEMPO adds
Dosage is the 0.01%-1% of vegetable-fibre slurry absolute dry mass, and the addition of cocatalyst is
The 0.1%-10% of vegetable-fibre slurry absolute dry mass, the addition of oxidant are plant fiber pulp
The 1.5%-150% of material absolute dry mass.Solve fibre process use equipment can be trough-style pulp beater,
PFI mill (beating machine or vertical beating machine), in highly concentrated single-deck or double disc refiner.Add
During TEMPO catalytic oxidation system, the pH value of this slurry system is preferably maintained at 10-10.5.
The regulation of pH can use hydrochloric acid solution and sodium hydroxide solution.
During solution fibre, the release effect to fiber finer cell wall improves TEMPO oxidation system
Accessibility, improve the efficiency of oxidation reaction；The carboxylic produced in simultaneous oxidation course of reaction
Base promotes the swollen of fiber the most in turn, promotes the dissociation process of fiber.
(4) it is preferably when vegetable-fibre slurry freedom reaches 150-450ml(
Time 200-400ml), filter plant is utilized to separate the fiber after aoxidizing and oxidized waste water；And it is right
Oxidized fibre after separation washs.Washing times is preferably 3-5 time.
Oxidation slurry carries out dehydration when freedom is higher separate, it is to avoid stock freeness
The separation difficulty of oxidation slurry and oxidized waste water time the lowest, it is easy to the recovery of medicine.
(5) oxidized fibre after washing again is inserted in the fine equipment of solution and is carried out solving fine process extremely
Freedom reaches 50ml and following, obtains the oxidized fibre after solving fibre.
(6) oxidized fibre after solving fibre is diluted to the concentration of 0.1%-10%, utilizes nanometer
Change equipment carries out nanorize process, i.e. obtains transparent homogeneous nanofiber cellulose solution.This is received
Riceization equipment can be high pressure homogenizer, microfluidization device or processor for ultrasonic wave.
The carboxyl-content of the nano-cellulose that the method prepares is 0.2-1.5mmol/g, and chi
Very little homogeneous, stable storage.
The present invention completes slurry during fiber carries out pre-solution fibre simultaneously
TEMPO aoxidizes, and utilizes and improves the release effect of fiber finer cell wall during solving fibre
The accessibility of TEMPO oxidation system, improves the efficiency of oxidation reaction；Simultaneous oxidation is reacted
During the carboxyl that produces promote the swollen of fiber the most in turn, promote dissociating of fiber
Process.Separate additionally, due to oxidation slurry being carried out when freedom is higher dehydration, it is to avoid
The separation difficulty of oxidation slurry and oxidized waste water when stock freeness is the lowest, it is easy to returning of medicine
Receive.The method is easier to realize waste water and separates and while chemical drugs recovery, can save and beat
Slurry energy consumption 20%-82%, and be easier to obtain size uniformity, nano-cellulose with low cost.
Below by specific embodiment, the present invention is described further.
Comparative example
Take 360g softwood Pulp Fibers (oven dry stock) to be placed in trough-style pulp beater, discongest
After 30min, apply 2kg stone roller and pull an oar.Solving 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
Under 90MPa, nanorize process 35pass obtains the nanofiber cellulose solution of transparent and homogeneous.
Note: adding top is the operation for beater, the purpose adding top is certain in order to apply
Beating pressure, fiber is cut off or wire-dividing broom purification under a certain pressure.Cellulose need through
Repeatedly just can get nano-cellulose after circular treatment, handled sample is all equal through high pressure
It is once 1pass that matter processes.
Embodiment 1
Take 360g softwood Pulp Fibers (oven dry stock) to be placed in trough-style pulp beater, discongest
After 30min, add the NaClO solution (matter of the NaBr, 60ml of the TEMPO, 24g of 2g
Amount percentage concentration is 10%, containing about 6.6g over dry NaClO), apply 2kg stone roller and pull an oar,
Oxidized fibre and waste water is separated when 190min disposed slurry freedom is 295ml.After washing 4 times
Oxidized fibre continue making beating to freedom be 50ml, the carboxyl-content of the oxidized fibre obtained
For 0.21mmol/g, oxidized fibre utilizes high pressure homogenizer nanorize under 90MPa to process
28pass obtains the nanofiber cellulose solution of transparent and homogeneous.
Compared with comparative example, the present embodiment solution fibre pretreatment energy consumption reduces by 20.8%, nanorize
Process and save energy consumption 20%.
Note: the beating equipment identical with comparative example use because of embodiment and nanorize equipment,
Same plant capacity, therefore embodiment is with comparative example, and making beating to identical freedom spends
The explanation of time length solve the height of fine energy consumption, nanorize obtains the nanofiber of transparent and homogeneous
The height of how many explanation nanorize energy consumptions of cellulose solution spent pass number.
Embodiment 2
Take 360g softwood Pulp Fibers (oven dry stock) to be placed in trough-style pulp beater, discongest
After 30min, add the NaClO solution of the NaBr, 1250ml of the TEMPO, 24g of 2g
(mass percentage concentration is 10%, containing about 137.5g over dry NaClO), apply 2kg cut or polish jade with an emery wheel into
Row making beating, separates oxidized fibre and waste water when 120min disposed slurry freedom is 305ml.Wash
Wash the oxidized fibre after 4 times continuing making beating to freedom is 50ml, the oxidized fibre obtained
Carboxyl-content is 0.82mmol/g, and oxidized fibre utilizes high pressure homogenizer nanometer under 90MPa
Change processes 12pass and obtains the nanofiber cellulose solution of transparent and homogeneous.
Compared with comparative example, the present embodiment solution fibre pretreatment energy consumption reduces by 50%, at nanorize
Reason saves energy consumption 85.7%.
Embodiment 3
Take 360g softwood Pulp Fibers (oven dry stock) to be placed in trough-style pulp beater, discongest
After 30min, add the NaClO solution of the NaBr, 2500ml of the TEMPO, 24g of 2g
(mass percentage concentration is 10%, containing about 275g over dry NaClO), applies 2kg stone roller and carries out
Making beating, separates oxidized fibre and waste water when 45min disposed slurry freedom is 240ml.Washing
It is 50ml to freedom that oxidized fibre after 4 times continues making beating, the oxidized fibre carboxyl obtained
Content is 1.45mmol/g, and oxidized fibre utilizes high pressure homogenizer at nanorize under 90MPa
Reason 3pass obtains the nanofiber cellulose solution of transparent and homogeneous.
Compared with comparative example, the present embodiment solution fibre pretreatment energy consumption reduces by 81.3%, nanorize
Process and save energy consumption 91.4%.
It addition, those skilled in the art also can be in the claims in the present invention scope of disclosure and essence
Make the various amendments in other form and details in god, add and replace.Certainly, these depend on
The various amendments made according to present invention spirit, add and the change such as replacement, all should be included in this
Invent within the scope of claimed.
Claims (8)
1. the method preparing nano-cellulose, it comprises the steps:
Vegetable-fibre slurry is provided；
Vegetable-fibre slurry is discongested and makes Plant fiber be separated into single fiber；
Vegetable-fibre slurry after discongesting carries out the pre-fibre that solves process, add TEMPO catalytic oxidation system while pre-solution fibre and fiber is aoxidized；
When vegetable-fibre slurry freedom reaches 150-450mL, separate the fiber after oxidation and waste water；
Fiber after oxidation is solved again fine process to freedom and reaches 50mL and the following oxidized fibre obtained after solving fibre；
Oxidized fibre after solving fibre is diluted to the concentration of 0.1-10%, the oxidized fibre after solving fibre is carried out nanorize process, obtains nanofiber cellulose solution；
Wherein, this TEMPO catalytic oxidation system includes TEMPO, cocatalyst and oxidant, and wherein TEMPO is 2,2,6,6-tetramethyl-1-piperidines-N-oxygen-derived free radicals and derivants thereof, and the addition of TEMPO is the 0.01%-1% of vegetable-fibre slurry absolute dry mass；Cocatalyst is one or more in metal bromide, metal iodide, metal borate compound, and cocatalyst addition is the 0.1%-10% of vegetable-fibre slurry absolute dry mass；Oxidant is sodium hypochlorite, and the addition of oxidant is the 1.5%-150% of vegetable-fibre slurry absolute dry mass；
Wherein, solve fibre process use equipment be trough-style pulp beater, PFI mill, in highly concentrated single-deck or double disc refiner.
The method preparing nano-cellulose the most as claimed in claim 1, it is characterised in that: this Plant fiber is at least one in softwood, broadleaf, grass family raw material.
The method preparing nano-cellulose the most as claimed in claim 1, it is characterised in that: the equipment that the step discongesting vegetable-fibre slurry uses is fluffer or hydrabrusher.
The method preparing nano-cellulose the most as claimed in claim 1, it is characterised in that: the time of discongesting of the step discongesting vegetable-fibre slurry is 10-30min.
The method preparing nano-cellulose the most as claimed in claim 1, it is characterised in that: when adding TEMPO catalytic oxidation system, the pH value of this slurry system is 10-10.5.
The method preparing nano-cellulose the most as claimed in claim 1, it is characterised in that: when vegetable-fibre slurry freedom reaches 200-400mL, separate the fiber after oxidation and waste water.
The method preparing nano-cellulose the most as claimed in claim 1, it is characterised in that: after separating the fiber after oxidation and waste water, the fiber after oxidation need to be washed and solve fine process again.
The method preparing nano-cellulose the most as claimed in claim 1, it is characterised in that: the equipment that the step that nanorize processes uses is high pressure homogenizer, microfluidization device or processor for ultrasonic wave.
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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 |
| 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 |
| CN105568728B (en) * | 2015-12-03 | 2017-05-31 | 汕头市雪果制衣实业有限公司 | A kind of method that nettle stalk prepares nano-cellulose |
| CN105566502B (en) * | 2015-12-21 | 2018-06-26 | 同济大学 | The preparation method of the renewable nano-cellulose film of water resistance |
| KR102415082B1 (en) | 2016-05-25 | 2022-06-29 | 사피 네덜란드 서비시즈 비.브이. | Preparation of chemically modified 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 |
| 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 |
| CN113774711B (en) * | 2021-10-07 | 2022-07-22 | 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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