CN103061174B - The method preparing cellulose nanometer fibril is assisted in a kind of strong acid preliminary treatment - Google Patents
The method preparing cellulose nanometer fibril is assisted in a kind of strong acid preliminary treatment Download PDFInfo
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Abstract
The method preparing cellulose nanometer fibril is assisted in a kind of strong acid preliminary treatment, first utilize the 60-70wt% concentrated sulfuric acid or hydrochloric acid, under 40-60 DEG C of condition, bleached pulp fibers is hydrolyzed preliminary treatment 1.0-1.5h, swollen, dissolve and open cellulosic sections amorphous region, then utilizing high speed homogenisation mechanical shearing to obtain cellulose nanometer fibril fast.The cellulose nanometer fibril production process energy consumption obtained by this method reduces, fibre crystallinity is high, Fiber Aspect Ratio is large, Heat stability is good, can be widely used in the fields such as reinforced composite, dust-absorbing filtering material, Ecosystem environmental protection material and bio-medical material.
Description
Technical field
The present invention relates to a kind of preparation method of string nanofibrils material, be specially a kind of strong acid preliminary treatment and assist the method preparing cellulose nanometer fibril.
Background technology
In recent years, plant base nanofiber is quietly promoting the fast development in the fields such as polymer composites, package decoration material, energy-conserving and environment-protective material, processing biopharmaceutical materials, conduction material.Cellulose nanometer fibril, as the important nano-fiber material of a class, often utilizes high speed machine to shear or the method for chemical oxidation, is separated by the cellulose microfibril in string and disassembles into the elongated fibers of diameter at nanoscale (lower than 100nm).This nanofiber has excellent mechanical property, and elastic modelling quantity is up to 100GPa; Also there is very high draw ratio, and its draw ratio is usually more than 100 simultaneously.With regard to nanostructured, in the dry state, nanofibrils forms natural Nanostructure Network to this nanofiber, can effectively stop small-molecule substance as the infiltration of water, oxygen, carbon dioxide, in addition, nanofibrils also has good light transmission and heat endurance.
Because prepared by chemical oxidation, the cost of cellulose nanometer fibril is higher, complex procedures, and its large-scale commercial is produced or is processed as master with mechanical shearing.In order to common bleached pulp fibers is cut into nanofibrils, need mechanical shearing repeatedly in process, cause energy consumption comparatively large, production cost is also higher, and these have become the major technology bottleneck of the rapid development of constraints on fiber element nanofibrils.Therefore, suitable preliminary treatment is carried out to starting pulps, improve fiber nanometer and disassemble efficiency, be of great immediate significance and application prospect, have immeasurable effect for the development promoting nanofiber and biomass nano material.
Summary of the invention
Technical problem solved by the invention is to provide a kind of strong acid preliminary treatment to assist the method preparing cellulose nanometer fibril, to solve the shortcoming in above-mentioned background technology.
Technical problem solved by the invention realizes by the following technical solutions:
The method preparing cellulose nanometer fibril is assisted in a kind of strong acid preliminary treatment, the distinguishing feature being different from other technique introduces strong acid hydrolysis preliminary treatment bleached pulp fibers, swollen, dissolve and open cellulosic sections amorphous region, then utilize high speed homogenisation mechanical shearing to obtain cellulose nanometer fibril fast, comprise the following steps:
1st step: by bleached pulp fibers swollen 24h in deionized water, then high-speed stirred dispersion 0.5h, is adjusted to the suspension solution of mass fraction of solids 1.5 ~ 2.0%.This mixed liquor shears 3 ~ 5 times repeatedly through ultra-fine colloid mill again, swollenization and cut short raw fiber.Fine grinding fiber solution to be removed after supernatant liquid high speed centrifugation again and is dried after centrifugation.
2nd step: the fiber after drying carries out the concentrated sulfuric acid or concentrated hydrochloric acid hydrolysis, the concentration of acid is 60 ~ 70wt%, acidolysis time 1.0 ~ 1.5h, and acidolysis temperature controls at 40 ~ 60 DEG C, and fiber is 2 ~ 8g/ml with matching well of acid solution of hydrolysis.
3rd step: acid hydrolysis solution is washed to neutrality repeatedly, first adds in a certain amount of alkali and unreacted acid, then through Buchner funnel by pretreatment of fiber deionized water washing repeatedly.Fiber centrifugation after washing is adjusted to solid content 1.5 ~ 2.0%.
4th step: the high-strength mechanical shearing processing of pretreatment of fiber high pressure.Acidolysis pretreatment of fiber solution mechanical shearing process in microjet high pressure homogenizer after washing, wherein shears 10 times at 200 μm of reaction chamber Inner eycle, then shears 5 times in 87 μm of reaction chambers, namely plastic.
In the present invention, in described 1st step process, the running speed of ultra-fine colloid mill is 2000 ~ 3000 rpm, and mill spacing is-0.2 ~ 0.4mm.
In the present invention, the fine grinding fiber moisture 10 ~ 18% in described 1st step process after centrifuge dripping.
In the present invention, in described 2nd step process, acid hydrolytic reaction completes in constant-temperature table, shaking speed 150 ~ 250rpm.
In the present invention, in described 2nd step process, fiber and acid refer to hydrochloric acid or the sulfuric acid of the fine grinding fiber after drying and 60 ~ 70wt% respectively, and its ratio is 2 ~ 8g/ml.
In the present invention, in described 3rd step process, alkali is sodium hydroxide solution, and alkali concn is 15 ~ 20%.
In the present invention, in described 3rd step process, the rotating speed of centrifugation is 3000 ~ 35000 rpm, removing upper strata centrifugate.
In the present invention, in described 4th step process during microjet high pressure homogenizer shear treatment, in 200 μm of reaction chambers, pressure is 35 ~ 40MPa, and in 87 μm of reaction chambers, pressure is 140 ~ 150MPa.
Beneficial effect: of the present invention is that the method preparing cellulose nanometer fibril is assisted in a kind of strong acid preliminary treatment.By strong acid hydrolysis preliminary treatment bleached pulp fibers, swollen, dissolve and open cellulosic sections amorphous region, then utilizing high speed homogenisation mechanical shearing to obtain cellulose nanometer fibril fast.The method can not only reduce the energy consumption of cellulose nanometer fibril preparation process, and strong acid hydrolysis can improve cellulosic degree of crystallinity simultaneously, improves the mechanical strength of nanofiber to a certain extent.Therefore, the cellulose nanometer fibril obtained by the method can be widely used in the fields such as reinforced polymeric material, dust-absorbing filtering material, Ecosystem environmental protection material and bio-medical material.
Detailed description of the invention
Give an actual example below and describe the present invention.
The technological means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with specific embodiment, setting forth the present invention further.
Embodiment 1:
1st step: by bleached pulp fibers swollen 24h in deionized water, then high-speed stirred dispersion 0.5h, is adjusted to the suspension solution of mass fraction of solids 1.5%.This mixed liquor shears 3 times repeatedly through ultra-fine colloid mill again, swollenization and cut short raw fiber; Speed of grinding plate 2500 rpm, mill spacing is ~ 0.1mm.Pre-grinding fiber solution to be removed after supernatant liquid high speed centrifugation again and is dried to moisture content 12% after centrifugation.
2nd step: the fiber after drying carries out concentrated sulfuric acid hydrolysis, the concentration of acid is 64wt%, acidolysis time 1.5h, and acidolysis temperature controls at 50 DEG C, and fiber matches well as 4g/ml with hydrolysis acid solution.Acidolysis reaction completes in constant temperature (set temperature 50 DEG C) shaking table, shaking speed 180rpm.
3rd step: acid hydrolysis solution is washed to neutrality repeatedly, first adds in a certain amount of 15% sodium hydroxide solution and unreacted acid, then through Buchner funnel by pretreatment of fiber deionized water washing repeatedly.Fiber centrifugation after washing is adjusted to solid content 1.5%.
4th step: the high-strength mechanical shearing processing of pretreatment of fiber high pressure.Acidolysis pretreatment of fiber solution mechanical shearing process in microjet high pressure homogenizer after washing, wherein shears 10 times at 200 μm of reaction chamber Inner eycle, then shears 5 times in 87 μm of reaction chambers, namely plastic.
Embodiment 2:
1st step: by bleached pulp fibers swollen 24h in deionized water, then high-speed stirred dispersion 0.5h, is adjusted to the suspension solution of mass fraction of solids 2.0%.This mixed liquor shears 4 times repeatedly through ultra-fine colloid mill again, swollenization and cut short raw fiber; Speed of grinding plate 3000 rpm, mill spacing is ~ 0.1mm.Pre-grinding fiber solution to be removed after supernatant liquid high speed centrifugation again and is dried to moisture content 16% after centrifugation.
2nd step: the fiber after drying carries out concentrated sulfuric acid hydrolysis, the concentration of acid is 70wt%, acidolysis time 1.0h, and acidolysis temperature controls at 55 DEG C, and fiber matches well as 6g/ml with hydrolysis acid solution.Acidolysis reaction completes in constant temperature (set temperature 55 DEG C) shaking table, shaking speed 180rpm.
3rd step: acid hydrolysis solution is washed to neutrality repeatedly, first adds in a certain amount of 16% sodium hydroxide solution and unreacted acid, then through Buchner funnel by pretreatment of fiber deionized water washing repeatedly.Fiber centrifugation after washing is adjusted to solid content 2.0%.
4th step: the high-strength mechanical shearing processing of pretreatment of fiber high pressure.Acidolysis pretreatment of fiber solution mechanical shearing process in microjet high pressure homogenizer after washing, wherein shears 10 times at 200 μm of reaction chamber Inner eycle, then shears 5 times in 87 μm of reaction chambers, namely plastic.
Embodiment 3:
1st step: by bleached pulp fibers swollen 24h in deionized water, then high-speed stirred dispersion 0.5h, is adjusted to the suspension solution of mass fraction of solids 2%.This mixed liquor shears 5 times repeatedly through ultra-fine colloid mill again, swollenization and cut short raw fiber; Speed of grinding plate 3000 rpm, mill spacing is ~ 0.1mm.Pre-grinding fiber solution to be removed after supernatant liquid high speed centrifugation again and is dried to moisture content 18% after centrifugation.
2nd step: the fiber after drying carries out concentrated hydrochloric acid hydrolysis, the concentration of acid is 70wt%, acidolysis time 1.5h, and acidolysis temperature controls at 50 DEG C, and fiber matches well as 8g/ml with hydrolysis acid solution.Acidolysis reaction completes in constant temperature (set temperature 50 DEG C) shaking table, shaking speed 200rpm.
3rd step: acid hydrolysis solution is washed to neutrality repeatedly, first adds in a certain amount of 20% sodium hydroxide solution and unreacted acid, then through Buchner funnel by pretreatment of fiber deionized water washing repeatedly.Fiber centrifugation after washing is adjusted to solid content %.
4th step: the high-strength mechanical shearing processing of pretreatment of fiber high pressure.Acidolysis pretreatment of fiber solution mechanical shearing process in microjet high pressure homogenizer after washing, wherein shears 10 times at 200 μm of reaction chamber Inner eycle, then shears 5 times in 87 μm of reaction chambers, namely plastic.
More than show and describe general principle of the present invention and principal character and advantage of the present invention; the technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and description just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications; these changes and improvements all fall in the claimed scope of the invention, and application claims protection domain is defined by appending claims and equivalent thereof.
Claims (5)
1. the method preparing cellulose nanometer fibril is assisted in strong acid preliminary treatment, and its feature is, comprises the following steps:
1st step: by bleached pulp fibers swollen 24h in deionized water, then high-speed stirred dispersion 0.5h, be adjusted to the suspension solution of mass fraction of solids 1.5 ~ 2.0%, this suspension solution shears 3 ~ 5 times repeatedly through ultra-fine colloid mill again, swollenization and cut short raw fiber, pre-grinding fiber solution remove supernatant liquid after centrifugation after again high speed centrifugation dry, wherein, the running speed of ultra-fine colloid mill is 2000 ~ 3000 rpm, and mill spacing is-0.2 ~ 0.4mm;
2nd step: the fiber after drying carries out the concentrated sulfuric acid or concentrated hydrochloric acid hydrolysis, the concentration of acid is 60 ~ 70wt%, acidolysis time 1.0 ~ 1.5h, and acidolysis temperature controls at 40 ~ 60 DEG C, and fiber is 2 ~ 8g/ml with matching well of acid solution of hydrolysis;
3rd step: acid hydrolysis solution is washed to neutrality repeatedly, first adds in a certain amount of alkali and unreacted acid, then through Buchner funnel by pretreatment of fiber deionized water washing repeatedly, the fiber centrifugation after washing is adjusted to solid content 1.5 ~ 2.0%;
4th step: the high-strength mechanical shearing processing of pretreatment of fiber high pressure, acidolysis pretreatment of fiber solution mechanical shearing process in microjet high pressure homogenizer after washing, wherein shear 10 times at 200 μm of reaction chamber Inner eycle, again in 87 μm of reaction chambers shear 5 times namely plastic, during microjet high pressure homogenizer shear treatment, in 200 μm of reaction chambers, pressure is 35 ~ 40MPa, and in 87 μm of reaction chambers, pressure is 140 ~ 150MPa.
2. the method preparing cellulose nanometer fibril is assisted in a kind of strong acid preliminary treatment according to claim 1, it is characterized in that, the fine grinding fiber moisture 10 ~ 18% in described 2nd step after centrifuge dripping.
3. the method preparing cellulose nanometer fibril is assisted in a kind of strong acid preliminary treatment according to claim 1, it is characterized in that, in described 2nd step, acid hydrolytic reaction completes in constant-temperature table, shaking speed 150 ~ 250rpm.
4. the method preparing cellulose nanometer fibril is assisted in a kind of strong acid preliminary treatment according to claim 1, it is characterized in that, in described 3rd step, alkali is sodium hydroxide solution, and alkali concn is 10 ~ 20%.
5. the method preparing cellulose nanometer fibril is assisted in a kind of strong acid preliminary treatment according to claim 1, it is characterized in that, in described 3rd step, the rotating speed of centrifugation is 3000 ~ 35000 rpm, removing upper strata centrifugate.
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| US9322133B2 (en) * | 2012-11-30 | 2016-04-26 | Api Intellectual Property Holdings, Llc | Processes and apparatus for producing nanocellulose, and compositions and products produced therefrom |
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| CN108219008A (en) * | 2018-01-25 | 2018-06-29 | 陕西科技大学 | Nano cellulose crystal and method prepared by acid hydrolyzed cellulose microfibril |
| CN108486671B (en) * | 2018-03-28 | 2020-07-28 | 华南理工大学 | High-water-retention plant cellulose micro/nano fibril and preparation method and application thereof |
| CN112725917B (en) * | 2020-12-28 | 2023-07-04 | 海南华创槟榔研究院 | Preparation method of betel nut seed cellulose nanofibrils |
| CN113123159B (en) * | 2021-04-09 | 2022-11-22 | 陕西科技大学 | Cellulose nano-fibril suspension and preparation method thereof |
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