CN104072787A - Method for preparing high-concentration nanocellulose colloid - Google Patents
Method for preparing high-concentration nanocellulose colloid Download PDFInfo
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- CN104072787A CN104072787A CN201410297896.4A CN201410297896A CN104072787A CN 104072787 A CN104072787 A CN 104072787A CN 201410297896 A CN201410297896 A CN 201410297896A CN 104072787 A CN104072787 A CN 104072787A
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Abstract
The invention discloses a method for preparing a high-concentration nanocellulose colloid. The method comprises the following steps: preparing nanocellulose by adopting a mechanical process, a chemical process, a biological process or a mechanochemical process, and centrifuging or filtering the obtained nanocellulose by microporous filter cloth to separate the nanocellulose from reaction deposits to prepare nanocellulose colloid; freezing the nanocellulose colloid at low temperature to gather and entangle the nanocellulose; unfreezing the frozen nanocellulose colloid at the temperature of more than 0 DEG C to deposit the gathered and entangled nanocellulose; performing filtering, pressure filtering and washing on the deposits to obtain a product, and dispersing the product in a solvent under the mechanical shear effect to obtain the high-concentration nanocellulose colloid. According to the method, the effects of purifying and concentrating the nanocellulose colloid at the same time can be achieved, the operating steps can be reduced, the production cycle of the nanocellulose is greatly shortened, and the cost of the nanocellulose is greatly lowered; the method is easy to popularize and apply.
Description
Technical field
The invention belongs to field of nano material preparation, particularly a kind of method of preparing highly concentrated nano cellulose colloid.
Background technology
In order to alleviate and to solve world today's greenhouse gases, the energy and resource exhaustion, the significant problem such as environmental pollution is serious, develop renewable circulation, environmental protection, degradable material has become much-talked-about topic, expects that it can replace take the use of fossil energy as basic material in some aspects.
Nano-cellulose is that natural plant fibre passes through mechanical process [A.N.Nakagaito, et al.Appl.Phys.A 78, 547-552 (2004)], chemical method [Robert J.Moon, et al.Chem.Soc.Rev., 2011, 40, 3941-3994], force chemistry [Yong Huang, ChemSus Chem 2012, 5, 2319-2322] etc. means obtain there is high length-diameter ratio, high-specific surface area, high strength (Young's modulus is about 110 ~ 220 Gpa), have than the nano material of the high Young's modulus of kevlar fiber and the thermal expansivity lower than general pottery [Wang Shiwen etc. Science Bulletin, 2013, 24:2385-2392.], have physiologically acceptable concurrently simultaneously, sustainable, degradable, the advantages such as environmental protection.
By acid-hydrolysis method [Q. Q. Wang et al.Cellulose (2012) 19:2033-2047], TEMPO is oxidized [Akira Isogai, et al. Biomacromolecules, 2006, 7 (6): 1687-1691], grafting chloroactic acid method [Lars W gberg, et al.Langmuir2008, 24, 784-795], periodate oxidation method [Henrikki Liimatainen, et al.Cellulose (2013) 20:741-749] etc. in the nano-cellulose colloid last handling process prepared of method because needs are separated from reactant by the method such as centrifugal, again through purification process such as dialysis deionizations, the solid content that obtains the nano-cellulose colloid that neutral foreign matter content is few is lower.Nano-cellulose after dry through ordinary method, due to effects such as intermolecular easy formation hydrogen bond and entanglement, thus be just difficult to its redispersion in water, so can only preserve with the form of colloid at present.But compared with the nano-cellulose of low-solid content, in long-range transportation and delivery process, will certainly increase the cost of nano-cellulose, limit its application.Chinese invention patent application [application number 201,310,236 188.5] discloses a kind of preparation method of highly concentrated nano cellulose colloid, it passes through to control rotary evaporation processing condition by the nano-cellulose colloid of lower concentration, temperature (30-50 ℃), rotating speed (2-6rpm) concentrates the nano-cellulose colloid of preparation high density (massfraction 40% and above concentration).But before this method is concentrated, nano-cellulose colloid must fall the ion dialyses in solution, just can concentrate.Dialysis procedure length consuming time, the production cost of increase nano-cellulose.
Summary of the invention
The object of the invention is to overcome the deficiency of existing nano-cellulose concentration technique, a kind of method of preparing highly concentrated nano cellulose colloid is provided.
Concrete steps are:
(1) by mechanical process, chemical method, biological process or force chemistry, prepare nano-cellulose, gained nano-cellulose, by centrifugal or micropore filter-cloth filtering, is separated itself and throw out, makes nano-cellulose colloid.
(2) nano-cellulose colloid cryogenic freezing step (1) being made is frozen, and makes in freezing freezing process, to form and assemble and tangle between nano-cellulose; Then, freezing icing nano-cellulose colloid is placed on to 0 ℃ and thaws above, the nano-cellulose of assembling and tangling is precipitated; Then, by throw out, by filtration, press filtration and carrying out washing treatment, products therefrom is scattered in solvent under mechanical shearing effect, makes highly concentrated nano cellulose colloid.
The aperture of described micropore filter cloth is 0.001 ~ 1 micron.
Described mechanical shearing effect comprises high speed machine paddling process, high pressure homogenizer homogenizing method, ball milled, mill method and ultrasonic dispersion.
Described solvent is a kind of in water, dimethyl formamide, dimethyl sulfoxide (DMSO), acetone, acetonitrile, tetrahydrofuran (THF), methacrylic acid, dioxane and aniline.
The present invention compared with prior art, has the following advantages and beneficial effect:
(1) the inventive method can reach the effect of Simultaneous purification and concentrated nano-cellulose colloid, and do not need to remove with dialysis acid, alkali or other chemical reagent producing in nano-cellulose colloid preparation process, the step that simplifies the operation, reduces production cycle and the cost of nano-cellulose greatly.
(2) preparation method of the required nano-cellulose colloid of the inventive method variation, is easy to apply.
Accompanying drawing explanation
Fig. 1 is the freeze concentration process photo that the embodiment of the present invention 1 makes nano-cellulose colloid, wherein: a is the nano-cellulose dispersion liquid (before freezing) after centrifugation; B is the nano-cellulose precipitation (after freezing) after freeze-thaw; C is the nano-cellulose colloid (massfraction 2.13wt%) after freeze concentration; D is the nano-cellulose colloid (massfraction 3.77wt%) after freeze concentration.
Fig. 2 is the freeze concentration process photo that the invention process 2 makes nano-cellulose colloid, and wherein A is the nano-cellulose dispersion liquid (before freezing) after centrifugation; B is the nano-cellulose precipitation (after freezing) after freeze-thaw; C is the nano-cellulose colloid (massfraction 0.49wt%) after freeze concentration.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, but the present invention is not limited to following instance.
embodiment 1:
(1) by sulfuric acid process (in chemical method a kind of), prepare nano-cellulose: first, the paper pulp fiber of over dry is mixed with certain density sulphuric acid soln, the liquor ratio of controlling paper pulp fiber and sulphuric acid soln is 1:9, controlling the mass concentration of sulfuric acid after mixing is 58%, then at room temperature infiltrate 30 minutes, transferred to again in reactor, controlling temperature is 55 ℃, react 10 hours, after reaction finishes, add wherein water stopped reaction, filter to obtain fiber, then fiber is dissociated into nano-cellulose under high-speed stirring, then centrifugal itself and the throw out of making is separated, the nano-cellulose colloid that makes low acidity (is shown in Fig. 1 a).
(2) the nano-cellulose colloid of low acidity step (1) being made freezes by refrigerator cryogenic freezing, makes in freezing freezing process, to form and assemble and tangle between nano-cellulose; Then, freezing icing nano-cellulose colloid is placed at 25 ℃ and is thawed, the nano-cellulose that makes to assemble and tangle precipitate (seeing b in Fig. 1), throw out is again by filtration, press filtration and carrying out washing treatment, products therefrom is distributed in water by high speed machine paddling process, and making massfraction is the neutral nano-cellulose colloid (seeing c in Fig. 1) of 2.13wt%.When massfraction is concentrated to 3.77wt%, nano-cellulose colloid is gel (seeing d in Fig. 1).
embodiment 2:
(1) by sodium chloroacetate method (in chemical method a kind of), prepare nano-cellulose: first, the paper pulp fiber of over dry is mixed with certain density NaOH solution, the liquor ratio of controlling paper pulp fiber and NaOH solution is 1:8, controlling the mass concentration of NaOH after mixing is 12%, then at room temperature infiltrate 30 minutes, transferred in reactor, adding massfraction is 95% industrial spirit, reaction is warming up to 75 ℃, add sodium chloroacetate (with the mass ratio of paper pulp fiber be 1:1.5), react 3 hours, after having reacted, with distilled water by product washes clean, then, it is mixed with water, regulating pH is alkalescence, under stirring, high speed machine makes nano-cellulose again, then with aperture, be the micropore filter-cloth filtering of 0.5 micron, itself and throw out are separated, make nano-cellulose colloid (seeing A in Fig. 2).
(2) nano-cellulose colloid step (1) being made freezes by refrigerator-freezer cryogenic freezing, makes in freezing freezing process, to form and assemble and tangle between nano-cellulose; Then, freezing icing nano-cellulose colloid is placed at 25 ℃ and is thawed, the nano-cellulose that makes to assemble and tangle precipitate (seeing B in Fig. 2), throw out is again by filtration, press filtration and carrying out washing treatment, products therefrom is distributed in water by ball milled, making massfraction is the neutral nano-cellulose colloid of 0.49wt%, is gel (seeing C in Fig. 2).
embodiment 3:
(1) by sodium periodate method (in chemical method a kind of), prepare nano-cellulose: preparation method is with reference to Henrikki Liimatainen et al.Cellulose (2013) 20:741-749, made product is the micropore filter-cloth filtering of 0.8 micron with aperture, itself and throw out are separated, make the nano-cellulose colloid of low acidity.
(2) the nano-cellulose colloid of low acidity step (1) being made freezes by refrigerator cryogenic freezing, makes in freezing freezing process, to form and assemble and tangle between nano-cellulose; Then, freezing icing nano-cellulose colloid is placed at 25 ℃ and is thawed, the nano-cellulose of assembling and tangling is precipitated, throw out is again by filtration, press filtration and carrying out washing treatment, products therefrom is distributed in water by high pressure homogenizer homogenizing method, makes highly concentrated nano cellulose colloid.
Obviously, the above embodiment of the present invention is only for example of the present invention is clearly described, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot give all embodiments exhaustive.Every still row in protection scope of the present invention of apparent variation that technical scheme of the present invention extends out or change that belong to.
Claims (1)
1. a method of preparing highly concentrated nano cellulose colloid, is characterized in that concrete steps are:
(1) by mechanical process, chemical method, biological process or force chemistry, prepare nano-cellulose, gained nano-cellulose, by centrifugal or micropore filter-cloth filtering, is separated itself and reaction precipitation thing, makes nano-cellulose colloid;
(2) nano-cellulose colloid cryogenic freezing step (1) being made is frozen, and makes in freezing freezing process, to form and assemble and tangle between nano-cellulose; Then, freezing icing nano-cellulose colloid is placed on to 0 ℃ and thaws above, the nano-cellulose of assembling and tangling is precipitated; Then, by throw out, by filtration, press filtration and carrying out washing treatment, products therefrom is scattered in solvent under mechanical shearing effect, makes highly concentrated nano cellulose colloid;
The aperture of described micropore filter cloth is 0.001 ~ 1 micron;
Described mechanical shearing effect comprises high speed machine paddling process, high pressure homogenizer homogenizing method, ball milled, mill method and ultrasonic dispersion;
Described solvent is a kind of in water, dimethyl formamide, dimethyl sulfoxide (DMSO), acetone, acetonitrile, tetrahydrofuran (THF), methacrylic acid, dioxane and aniline.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761648A (en) * | 2015-04-15 | 2015-07-08 | 桂林理工大学 | Method for preparing nanocellulose at low energy consumption |
| CN107460759A (en) * | 2017-08-18 | 2017-12-12 | 华南理工大学 | A kind of method for quickly purifying of nano-cellulose suspension |
| CN111172805A (en) * | 2020-01-10 | 2020-05-19 | 中国制浆造纸研究院有限公司 | Preparation method of biomass-based barrier coating |
| CN113150309A (en) * | 2021-03-26 | 2021-07-23 | 湖北福力德鞋业有限责任公司 | Method for modifying anionic waterborne polyurethane emulsion by carboxyl nanocellulose |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102899950A (en) * | 2012-10-25 | 2013-01-30 | 福建农林大学 | Method for preparing nano cellulose by simultaneous assistance of ultrasonic waves and microwaves |
| CN102977393A (en) * | 2012-11-30 | 2013-03-20 | 中南林业科技大学 | Preparation method of transparent waterproof plant nanometer fiber composite material |
| CN103304824A (en) * | 2013-06-15 | 2013-09-18 | 浙江理工大学 | Preparation method of high-concentration nano microcrystalline cellulose gel |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899950A (en) * | 2012-10-25 | 2013-01-30 | 福建农林大学 | Method for preparing nano cellulose by simultaneous assistance of ultrasonic waves and microwaves |
| CN102977393A (en) * | 2012-11-30 | 2013-03-20 | 中南林业科技大学 | Preparation method of transparent waterproof plant nanometer fiber composite material |
| CN103304824A (en) * | 2013-06-15 | 2013-09-18 | 浙江理工大学 | Preparation method of high-concentration nano microcrystalline cellulose gel |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761648A (en) * | 2015-04-15 | 2015-07-08 | 桂林理工大学 | Method for preparing nanocellulose at low energy consumption |
| CN107460759A (en) * | 2017-08-18 | 2017-12-12 | 华南理工大学 | A kind of method for quickly purifying of nano-cellulose suspension |
| CN107460759B (en) * | 2017-08-18 | 2020-12-22 | 华南理工大学 | Rapid purification method of nano-cellulose suspension |
| CN111172805A (en) * | 2020-01-10 | 2020-05-19 | 中国制浆造纸研究院有限公司 | Preparation method of biomass-based barrier coating |
| CN113150309A (en) * | 2021-03-26 | 2021-07-23 | 湖北福力德鞋业有限责任公司 | Method for modifying anionic waterborne polyurethane emulsion by carboxyl nanocellulose |
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Effective date of registration: 20170323 Address after: The Guangxi Zhuang Autonomous Region Qixing District, Guilin city 541004 Road No. 12 building of Guilin University of Technology innovation base business district 103 room Patentee after: Guilin Qi Hong Technology Co. Ltd. Address before: 541004 the Guangxi Zhuang Autonomous Region Guilin Construction Road No. 12 Patentee before: Guilin University of Technology |