CN102817276B - Method for preparing cellulose nano-grade filament film by using recovered waste paper - Google Patents
Method for preparing cellulose nano-grade filament film by using recovered waste paper Download PDFInfo
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- CN102817276B CN102817276B CN201210282759.4A CN201210282759A CN102817276B CN 102817276 B CN102817276 B CN 102817276B CN 201210282759 A CN201210282759 A CN 201210282759A CN 102817276 B CN102817276 B CN 102817276B
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- 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
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Abstract
The invention relates to a method for preparing a cellulose nano-grade filament film by using recovered waste paper. The method comprises the steps of chemical pretreatment, mechanical separation, and film preparation. The method has the advantages that: the film is prepared through a combination of acid-alkali pretreatment and wood powder grinding; lignin in the wood powder is removed mainly by using sodium chlorite in an acidic condition; hemicellulose in the wood powder is removed by using dilute potassium hydroxide, and the rest is substantially cellulose; and the cellulose is subjected to a fiber-opening process by using dilute hydrochloric acid. With the fiber-opening process, hydrogen bonding interactions in the filaments are reduced, such that biomass cellulose nano-grade filaments with high length-diameter ratios are obtained. Minerals in the fibers are removed through hydrochloric acid treatment, and alkali-insoluble hemicellulose in purified cellulose is affected, such that an effect of cellulose fiber purification is achieved. The chemical components are detected through Fourier transform infrared. The grinding treatment is simple and easy to operate, such that large-scale production can be carried out. An elastic modulus is 2901.14MPa, and a tensile strength is 63.26MPa.
Description
Technical field
What the present invention relates to is a kind of method that waste paper that utilizes recovery is prepared cellulose nanofibrils film.Belong to biomass nano fibre technology field.
Background technology
The separation process of biomass cellulose nanofibrils mainly comprises that preliminary treatment is separated with machinery.Two kinds of main processing modes in whole separation process, have been used: mechanical treatment and chemical treatment.Although consume certain energy in mechanical treatment, but can make full use of raw material; In chemical treatment, only utilized the raw material of half left and right, removed second half raw material, but the stirring in experiment will promote to generate chemical heat and effectively remove impurity, this combustion heat is the energy consuming in whole chemical action process.
A kind of method that has at present oxidation pre-treatment is that medium catalytic oxidation is prepared cellulose nanofibrils with TEMPO.TEMPO oxidation is a kind of good method of native cellulose surface modification, and natural fabric has been introduced carboxyl and aldehyde radical functional group in the environment of the gentle aqueous solution, and fiber prepared by this method is had relatively high expectations to raw-material selection.The form of the biomass cellulose nanofibrils after the oxidation of TEMPO medium does not change, oxidation only occurs on the surface of microfibril and makes it electronegative, between fibril and fibril, repel like this, thereby reduce the Hyarogen-bonding between fibril, fibrillation finally occurs.This method mild condition, has effectively removed lignin, but it becomes to produce high cost.
Another kind of employing prepared cellulose nanofibrils in conjunction with mechanical treatment and enzyme preliminary treatment, first with refiner, refines to increase the accessibility of cell membrane, and then carries out enzyme processing, and then fine grinding once, is finally poured cellulose slurry into homogeneous in high pressure homogenizer again.From cost and equipment angle, Biological Pretreatment has shown unique advantage, and available single-minded wooden enzyme treated feed stock is to decompose lignin and to improve lignin digestion rate, but it is very low after Biological Pretreatment, to be hydrolyzed yield.
Summary of the invention
The present invention proposes is a kind of method that waste paper that utilizes recovery is prepared cellulose nanofibrils film, adopts Chemical Pretreatment to prepare biomass cellulose nanofibrils in conjunction with mechanical phonograph recorder separation, then biomass cellulose nanofibrils turbid liquid is prepared into film.
The technology of the present invention solution: utilize waste paper to prepare the method for cellulose nanofibrils film, comprise following processing step, one, Chemical Pretreatment; Two, machinery is separated; Three, prepare film.
Good effect of the present invention: prepare cellulose nanofibrils in conjunction with grinding wood powder by acid-base pretreatment, what in acid-base pretreatment, use is all the soda acid aqueous solution that concentration is very low, gentle with respect to strong acid pretreatment reaction, mainly with sodium chlorite, under acid condition, remove the lignin in wood powder, with the potassium hydroxide of dilution, remove hemicellulose in wood powder again, remaining is cellulose substantially, finally with watery hydrochloric acid, cellulose is opened to fine processing.Opening fine processing is in order to reduce Hyarogen-bonding between fibril inside, thereby after mechanical treatment, is obtaining the biomass cellulose nanofibrils of high length-diameter ratio.Utilize after salt acid treatment, contribute to remove the mineral matter in fiber, in addition, salt acid treatment also can exert an influence by insoluble hemicellulose to the alkali in purifying cellulose, can play the effect that is further purified cellulose fibre.Chemical constituent in leaching process can detect by Fourier transform infrared.In mechanical treatment, milled processed is simple to operation, can produce in enormous quantities.The elastic modelling quantity of waste paper pulp fiber element nanofibrils film is 2901.14MPa, and TENSILE STRENGTH is 63.26MPa.
The specific embodiment
Embodiment
One, Chemical Pretreatment,
1) accurate weighing goes out the waste paper that 4g reclaims, and is dissolved in 150ml distilled water, with pulverizer, moistening reclaimed waste paper is ground into paper pulp;
2) in paper pulp, add 0.5ml glacial acetic acid and 0.6g sodium chlorite, with glass bar, stir, with preservative film, seal rim of a cup, put into 75 ℃ of thermostat water baths and heat 1h, in cup, putting into magnetite constantly stirs, make reaction more abundant, stir and within 1 hour, in backward beaker, continue to add 0.5ml glacial acetic acid and 0.6g sodium chlorite, continuation is heated at constant temperature 1h in 75 ℃ of water-baths, so repeat 2 times, until sample bleaches, then with vacuum filtration pump and Buchner funnel, filter, and constantly wash sample until filtered fluid becomes neutral with distilled water, to remove residual lignin in waste paper, obtain holocellulose fiber,
3) brown cellulose fibre is packed in 250ml beaker, pour 150ml mass concentration into and be 4% potassium hydroxide solution, with preservative film, seal and put into 90 ℃ of thermostat water baths after rim of a cup and heat 2h, and in cup, put into magnetite and constantly stir, stir after 2 hours and filter with vacuum filtration pump and Buchner funnel, and use distilled water cyclic washing, to remove the hemicellulose in brown cellulose, until filtered fluid becomes neutral for the first time;
4) will become for the first time neutral filtered fluid sample to be poured in 250ml beaker, adding 150ml mass concentration is 6% potassium hydroxide solution, with preservative film, seal rim of a cup, then put into 90 ℃ of water-bath heated at constant temperature 2h, and constantly stir with magnetite, stir after 2 hours and filter with vacuum filtration pump and Buchner funnel, and with distilled water cyclic washing for several times, until pH value, in 7 left and right, obtains purifying cellulose fiber like this;
5) purifying cellulose fiber is poured in 250ml beaker, adding 150ml concentration is 1% hydrochloric acid, with preservative film, seal rim of a cup, put into 80 ℃ of thermostat water baths and heat 2h, and stir with magnetite, then with vacuum filtration pump and Buchner funnel, filter, and use distilled water cyclic washing, until filtered fluid becomes neutral for the second time;
6) by becoming for the second time neutral filtered fluid to be configured to mass concentration, be 1% aqueous suspension, then carry out milled processed: between mill, gap is 0, grinding number of times is 30 times, and grinding rotating speed is 1500rpm, makes sample;
Two, machinery is separated, adopt polishing: the sample after Chemical Pretreatment is configured to after the turbid liquid of 1% mass concentration, join in the beaker of 250ml, the empty beaker of placing a 250ml at grinder discharging opening is to hold discharging sample, empty beaker will be immersed in the container that frozen water is housed, to prevent ground sample excess Temperature, degrade, open grinder switch, speed setting is 1500rpm, spin finishing rotating disk is apart from knob, when reaching 0, pours scale sample into, grind 30 times, make paper cellulose nanofibrils;
The described paper cellulose nanofibrils that makes, can make lignocellulosic nanofibrils by four kinds of diverse ways, the first, cellulose fibre is through grinder preliminary treatment 30min, obtain cellulose micrometer fibers element, utilize afterwards the ultrasonic processing 60min of cell pulverization machine (prior art), obtain paper cellulose nanofibrils; The second, cellulose fibre is through grinder preliminary treatment 30min, by the micrometer fibers element obtaining homogeneous 8 times in high pressure homogenizer (prior art), obtains lignocellulosic nanofibrils afterwards; The third, cellulose fibre obtains paper cellulose nanofibrils at grinding machine for grinding 60min; The 4th kind, cellulose fibre is preliminary treatment 60min in cell pulverization machine, and homogeneous 8 times in high pressure homogenizer, obtains paper cellulose nanofibrils afterwards.
With the wood fibre in mechanical separation method, remain water swollen state, to prevent the gathering between fibril.
Three, preparation film forming:
1) the paper cellulose nanofibrils after mechanical separation is got to 200ml;
2) utilize vacuum filtration pump and Buchner funnel to carry out suction filtration, sample forms paper cellulose nanofibrils film because of dehydration, and paper cellulose nanofibrils film diameter is 90mm;
3) with the paper cellulose nanofibrils film of two glass plate concora crush clampings, put into 55 ℃ of oven dry of drying box, 48 hours used times.
The elastic modelling quantity of paper cellulose nanofibrils film is 2901.14MPa, and TENSILE STRENGTH is 63.26MPa.
The application of nano-cellulose
Cellulose nanofibrils film is widely used as filler, to improve the performance such as intensity, toughness of plastics, rubber and other products.Aspect surface-functional and regulation and control, can be used for having hydrophobicity or hydrophilic biology sensor.Cellulose nanofibrils film can be for the protection housing of artificial skin, artificial blood vessel, nerve suture, training with fields such as micro-surgery models, animal wound dressings aspect medical science.Nano-cellulose is when doing cell engineering scaffold material, and its effect is to provide conductive performance and support structure, and improves the porous of support; In drug encapsulation, use, can control the transmission of active component.Polymer nanofiber material also can be used for human body skin wound and burn is processed, and also has unique performance as hemostatic material.Adopt the mode of electrostatic spinning biodegradable polymer to be directly sprayed on to the damage location of human body skin, form fibrous web-like wrapping layer, can promote skin histology grow and cicatrize a wound, can alleviate or eliminate the scar that traditional wound processing mode causes simultaneously.Optical property aspect, utilizes strengthening the property of it can develop novel flexible display, printed electronic device displays, solar cell, fuel cell, medical treatment transducer and precision optical instrument and accessory etc.Straw (containing cellulose) is used to producd fibers recently, and then is spun into fabric, similar cotton or flax, and can on common textile machinery, weave, with the cloth that feather and straw are produced, be applicable to carpet, automobile and building, cost is lower, and performance is better.
Claims (1)
1. utilize the waste paper of recovery to prepare a method for cellulose nanofibrils film, it is characterized in that the method comprises following processing step, one, Chemical Pretreatment; Two, machinery is separated; Three, prepare film;
Described Chemical Pretreatment processing step one, comprises
1) accurate weighing goes out 4g reclaimed waste paper, is dissolved in 150ml distilled water, with pulverizer, the waste paper of moistening recovery is ground into paper pulp;
2) in paper pulp, add 0.5ml glacial acetic acid and 0.6g sodium chlorite, with glass bar, stir, with preservative film, seal rim of a cup, put into 75 ℃ of thermostat water baths and heat 1h, in cup, putting into magnetite constantly stirs, make reaction more abundant, stir and within 1 hour, in backward beaker, continue to add 0.5ml glacial acetic acid and 0.6g sodium chlorite, continuation heated at constant temperature 1 hour in 75 ℃ of water-baths, so repeat 2 times, until sample bleaches, then with vacuum filtration pump and Buchner funnel, filter, and constantly wash sample until filtered fluid becomes neutral with distilled water, to remove residual lignin in reclaimed waste paper, obtain holocellulose fiber,
3) brown cellulose fibre is packed in 250ml beaker, pour 150ml mass concentration into and be 4% potassium hydroxide solution, with preservative film, seal and put into 90 ℃ of thermostat water baths after rim of a cup and heat 2 hours, and in cup, put into magnetite and constantly stir, stir after 2 hours and filter with vacuum filtration pump and Buchner funnel, and use distilled water cyclic washing, to remove the hemicellulose in brown cellulose, until filtered fluid becomes neutral for the first time;
4) will become for the first time neutral filtered fluid to be poured in 250ml beaker, adding 150ml mass concentration is 6% potassium hydroxide solution, with preservative film, seal rim of a cup, then put into 90 ℃ of water-bath heated at constant temperature 2h, and constantly stir with magnetite, stir after 2 hours and filter with vacuum filtration pump and Buchner funnel, and with distilled water cyclic washing for several times, until pH value 7 obtains purifying cellulose fiber like this;
5) purifying cellulose fiber is poured in 250ml beaker, adding 150ml concentration is 1% HCl, with preservative film, seal rim of a cup, putting into 80 ℃ of thermostat water baths heats 2 hours, and stir with magnetite, then with vacuum filtration pump and Buchner funnel, filter, and use distilled water cyclic washing, until filtered fluid becomes neutral for the second time;
6) by becoming for the second time neutral filtered fluid to make sample, to be configured to mass concentration be 1% aqueous suspension, then carries out milled processed: between mill, gap is 0, and grinding number of times is 30 times, and grinding rotating speed is 1500rpm, obtains sample;
Described mechanical separating technology step 2, adopt polishing: the sample after Chemical Pretreatment is configured to after the turbid liquid of 1% mass concentration, join in the beaker of 250ml, the empty beaker of placing a 250ml at grinder discharging opening is to hold discharging sample, empty beaker will be immersed in the container that frozen water is housed, to prevent ground sample excess Temperature, degrade, open grinder switch, speed setting is 1500rpm, spin finishing rotating disk is apart from knob, when reaching 0, pours scale sample into, grind 30 times, make paper cellulose nanofibrils; Fiber in mechanical separation method remains water swollen state, to prevent the gathering between fibril;
The described paper cellulose nanofibrils that makes, by four kinds of diverse ways, make paper cellulose nanofibrils, the first, cellulose fibre is through grinder preliminary treatment 30min, obtain cellulose micrometer fibers element, utilize afterwards the ultrasonic processing of cell pulverization machine 60min, obtain paper cellulose nanofibrils; The second, cellulose fibre is through grinder preliminary treatment 30min, by the micrometer fibers element obtaining homogeneous 8 times in high pressure homogenizer, obtains cellulose nanofibrils afterwards; The third, cellulose fibre obtains paper cellulose nanofibrils at grinding machine for grinding 60min; The 4th kind, cellulose fibre is preliminary treatment 60min in cell pulverization machine, and homogeneous 8 times in high pressure homogenizer, obtains paper cellulose nanofibrils afterwards;
The described membrane process step 3 that is prepared into, comprises
1) by the paper cellulose nanofibrils after mechanical separation, get 200ml;
2) utilize vacuum filtration pump and Buchner funnel to carry out suction filtration, sample forms paper cellulose nanofibrils film because of dehydration, and paper cellulose nanofibrils film diameter is 90mm;
3) with the paper cellulose nanofibrils film of two glass plate concora crush clampings, put into 55 ℃ of oven dry of drying box, dry 48 hours.
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| US10087580B2 (en) | 2015-05-01 | 2018-10-02 | Fpinnovations | Dry mixed re-dispersible cellulose filament/carrier product and the method of making the same |
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| CN103980545B (en) * | 2014-04-24 | 2016-07-06 | 江苏大学 | Utilize the method that waste paper prepares functional inorganic nano-cellulose composite |
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| CN110924238B (en) * | 2019-12-05 | 2021-09-03 | 安徽省农业科学院棉花研究所 | Preparation method of cotton cellulose nanofibril film |
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| CN101519812A (en) * | 2008-02-25 | 2009-09-02 | 李换位 | Process for manufacturing oxidized cellulose regenerated fibrils or thin films |
| CN101691698B (en) * | 2009-10-22 | 2012-05-02 | 东北林业大学 | Method for preparing lignocellulosic nanofibrils |
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