CN109705226A - A method of it is hydrolyzed using citric acid and ultrasonic wave added is combined to prepare carboxylated nano-cellulose - Google Patents
A method of it is hydrolyzed using citric acid and ultrasonic wave added is combined to prepare carboxylated nano-cellulose Download PDFInfo
- Publication number
- CN109705226A CN109705226A CN201811533245.5A CN201811533245A CN109705226A CN 109705226 A CN109705226 A CN 109705226A CN 201811533245 A CN201811533245 A CN 201811533245A CN 109705226 A CN109705226 A CN 109705226A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- citric acid
- nano
- fiber
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The method that the invention discloses a kind of to be hydrolyzed using citric acid and combine ultrasonic wave added preparation carboxylated nano-cellulose.Then this method is added in aqueous citric acid solution using bleached fiber pulpboard as substrate and carries out sour water solution, prepare Cellulose nanocrystal by ultrasound and centrifugation, then remaining solid fiber is prepared cellulose nanometer fibril by high pressure homogenizer.This method is green non-poisonous, time-consuming is short, preparation process risk is low, yield is higher and citric acid used is easily recycled, thus greatly reduces the cost of nano-cellulose preparation.In addition, the Cellulose nanocrystal and cellulose nanometer fibril dispersion stabilization with higher of preparation, excellent specific surface area, and carboxyl-content is higher, for nano-cellulose, further modification provides more chemistry routes.Finally, the nano-cellulose prepared does not have a residual of poisonous and harmful substance, thus using cellulose as the functionalization material of substrate in terms of, especially have wide practical use in terms of material relevant to human health.
Description
Technical field
The invention belongs to the green preparation fields of nano-cellulose, and in particular to a kind of to be hydrolyzed and combined super using citric acid
The method of sound auxiliary preparation carboxylated nano-cellulose.
Background technique
Cellulose is reserves natural polymer the most abundant in the most abundant renewable resource and nature on the earth
Compound is widely present in the cell walls such as various plants, algae, mushroom, have it is pollution-free, degradable, nontoxic, renewable,
The advantages that inexpensive and easily modified, is expected to the primary raw material for replacing petroleum to become the future world energy and chemical industry.
Nano-cellulose, refers to the cellulose that diameter arrives 100nm 1, can be divided into Cellulose nanocrystal body according to scale topography
And cellulose nanometer fibril.Cellulose nanocrystal body length is shorter, is obtained by the amorphous region of acid or enzyme hydrolysis cellulose
Length be 100nm-300nm or so rod-like fibre element；Nano-cellulose fiber length is longer, be it is several hundred to thousands of nanometers not
Deng reticulated cellulose, generally by Mechanical Method be made.
The nano-cellulose prepared by physically or chemically method, not only remains higher reactivity, while having prominent
Physical and chemical properties out, such as: there is nano-scale, excellent mechanical performance, higher Young's modulus, biggish compare table
Area, low thermal expansion coefficient etc., these performances make nano-cellulose have wide answer in terms of Materials Science and Engineering
Use prospect.Currently, the main preparation methods of Cellulose nanocrystal are to destroy the amorphous region of cellulose by mineral acid hydrolysis
And obtain, higher yield can be obtained, and method is increasingly mature.But at many aspects, there is also certain defects, for example, inorganic
Acid too strong, meeting excessive degradation cellulose is to damage the natural performance of nano-cellulose；Equipment can be corroded in preparation process,
And the filtrate that hydrolysis generates can not recycle, and generate a large amount of waste to damage to environment；Inorganic acid
It is expensive, it is larger to prepare risk, thus cause preparation cost higher, be not suitable for large-scale production；And by inorganic
Acid, such as the nano-cellulose of concentrated sulfuric acid preparation, surface has certain group, so that it is further to limit nano-cellulose
Functionalization utilizes.In recent years, using organic acid preparation Cellulose nanocrystal, there are also reports, however institute's report method is deposited extensively
The problems such as yield is lower, drug price is relatively high, organic acid used and additional catalyst are toxic, thus day of one's doom
Prepared nano-cellulose is made much with human health in relevant application, such as biomaterial, food packaging, shield
Skin and cosmetics etc., to be unable to reach the effective and green requirement for preparing nano-cellulose and later period value added applications.
Citric acid is largely present in many fruits and vegetables and animal as a kind of environmental-friendly organic monoacid
Bone, inside muscle and blood, can also promote the metabolism of human body, thus be widely used for food, beverage, medicine and
The industries such as cosmetics, price are relatively cheap and harmless.In the present invention, 95% or more citric acid can be in Nanowire
It after dimension element preparation, is recycled by crystallization and is utilized again, thus the cost for preparing nano-cellulose can be effectively reduced and subtract
Few influence to environment.In addition, there are three carboxylic acid groups for citric acid, there are many approach to react with cellulose, prepare
The nano-cellulose come also has higher carboxyl-content, in conjunction with original hydroxyl group, so that the nano-cellulose tool prepared
There are biggish functionalization potentiality.Moreover, achieving the purpose that carboxylated while citric acid hydrolysis, conventional nanofibers are eliminated
Element carry out carboxylated required for additional means and consumption, thus further greatly reduce nano-cellulose functionalization at
This.
At present about citric acid water solution combination ultrasonic wave added, high yield pulp1 step preparation carboxylated nano-cellulose method
There is not been reported.
Summary of the invention
Present invention is generally directed to various drawbacks existing during current nano-cellulose preparation method, provide a kind of environment
The method of friendly citric acid water solution combination ultrasonic wave added one-step preparation of carboxyl nano-cellulose.This method has raw material
The feature that source is extensive, preparation cost is low, the used time is relatively short, drug is Ke Xunhuanliyong, green non-poisonous and environment friendly and pollution-free.This
Outside, the nanofiber of this method preparation is known as relatively high yield, biggish specific surface area and more carboxyl-content, and produces
Product are nontoxic, thus are the functionalization material of cellulose base, are applied especially to establish in terms of the materials such as biomaterial, food, health care product
Basis is determined.
It is hydrolyzed the object of the present invention is to provide a kind of utilization citric acid and ultrasonic wave added is combined to prepare carboxylated nanofiber
The method of element, the nano-cellulose are easy to the further functionalization in later period.
Above-mentioned purpose of the present invention is to be achieved by the following technical programs.
A method of it is hydrolyzed using citric acid and ultrasonic wave added is combined to prepare carboxylated nano-cellulose, with bleached fiber
Pulpboard is substrate, is hydrolyzed by citric acid and the method for being aided with ultrasound prepares carboxylated nano-cellulose.
Preferably, the carboxylated nano-cellulose includes Cellulose nanocrystal and cellulose nanometer fibril.
Preferably, the citric acid is aqueous citric acid solution.
Preferably, the bleached fiber pulpboard is microcrystalline cellulose, bleaching bagasse pulp, bleached wood pulp, bleaching straw pulp, bleaching
One of cotton pulp, bleached bamboo pulp or several mixed bleach pulpboards.
Preferably, this method specifically comprises the following steps:
S1. citric acid is added to the water, forms aqueous citric acid solution after dissolution；
S2. over dry bleached fiber pulpboard is crushed, is added in aqueous citric acid solution under stirring conditions sufficiently reaction；
S3. reacted fibrous suspension is separated into fiber and filtrate by the method for vacuum filtration, with the method for revolving crystallization
Citric acid solid particle is recycled from filtrate；
S4. by the fiber isolated by be centrifuged method wash to neutrality, by ultrasound method by Cellulose nanocrystal most
It is detached from from fiber to bigization, then isolates Cellulose nanocrystal dispersion liquid with the method for centrifugation, by being freeze-dried or spraying
The Cellulose nanocrystal body of solid is obtained after mist is dry；
S5. fibre solid precipitating remaining after the separation of Cellulose nanocrystal body is prepared by cellulose by high-pressure nano homogenizer
Nanofibrils obtain the cellulose nanometer fibril of solid after freeze-drying or spray drying.
It is further preferred that the temperature of dissolution described in step S1 is 100 DEG C.
The speed stirred when it is further preferred that dissolving described in step S1 is 300r/min.
It is further preferred that the concentration of aqueous citric acid solution described in step S1 is 60 wt%-80 wt%.
It is further preferred that the revolving speed of stirring described in step S2 is 200r/min-400r/min, the time of reaction is 0.5-
4 hours, the temperature of reaction was 80 DEG C -120 DEG C.
It is further preferred that revolving described in step S3 is carried out under 70 DEG C, 60r/min.
It is further preferred that vacuum filtration G4 sand core funnel described in step S3.
It is further preferred that washing described in step S4 is that deionized water is added repeatedly to be centrifuged at 4000r/min to neutrality；
The power of ultrasound is 600W-1200W, there is the interval of 5s after the ultrasound that the time is the every 5s of 10-30min(), ultrasound 2 times.
It is further preferred that high-pressure nano homogenizer described in step S5 is D8(200nm) reaction under high pressure chamber, homogeneous 6-
7 times.
Compared with prior art, the present invention has the effect that
(1) citric acid is widely used in food, beverage, medicine and change as a kind of organic monoacid that common price is relatively cheap
Cosmetic industry, it is harmless, using citric acid hydrolysis prepare nano-cellulose with raw material sources extensively, preparation process risk
With the features such as at low cost, environment friendly and pollution-free, meet the requirement that sustainable production and environmental protection coexist.
(2) present invention is assisted using ultrasonic method, by the ultrasonic wave added of short period, will soon be fallen off after sour water solution
And the Cellulose nanocrystal not fallen off is laid and, and the yield of Cellulose nanocrystal is greatly improved.With traditional inorganic acids water
Solution prepares nano-cellulose and compares, and water consumption is less, without waste liquid and waste residue output；Nanowire is prepared with other organic acid hydrolysis
Dimension element is compared, and yield is higher, and does not need the auxiliary of catalyst, thus reduces the finished product of production, also reduces noxious material
Introducing.
(3) it by the energy consumption of the method for the present invention preparation cellulose nanometer fibril, is prepared than tradition machinery method low.
(4) citric acid used in the present invention can achieve 95% or more successful recycling.
(5) Cellulose nanocrystal and nanofibrils that the present invention prepares have lesser length and width dimensions, stable dispersion
Property, good material is provided in terms of being applied to Material reinforcement for the later period to be supported.
(6) nano-cellulose produced by the present invention carboxyl-content with higher reduces conventional nanofibers element carboxyl
More additional processes and chemical consumption, greatly reduce cost necessary to changing, simultaneously for the further functionalization of nano-cellulose
Extensive use provides more means approach.
Detailed description of the invention
Fig. 1 a is the atomic force electron microscope picture of prepared Cellulose nanocrystal.
Fig. 1 b is the atomic force electron microscope picture of prepared nanofibrils.
Specific embodiment
The contents of the present invention are further illustrated below with reference to specific example, but should not be construed as limiting the invention.?
In the case where without departing substantially from spirit of that invention and essence, to simple modifications or substitutions made by the method for the present invention, step or condition,
Belong to the scope of the present invention；Unless otherwise specified, what technological means used in embodiment was well known to those skilled in the art
Conventional means.
Unless stated otherwise, the present invention uses reagent, method and apparatus for the art conventional reagent, method and are set
It is standby.Unless stated otherwise, agents useful for same and material of the present invention are commercially available.
Embodiment 1: the nano-cellulose of citric acid water solution combination ultrasonic wave added one-step preparation of carboxyl
(1) 100 DEG C at a temperature of, the bleaching bagasse pulp plate of 5g over dry is crushed to the citric acid water for being added to that concentration is 80wt%
4h is reacted in solution (80g citric acid, 20ml deionized water), obtains hydrolysed suspension.
(2) hydrolysed suspension is filtered by vacuum to obtain solid fiber and filtrate by G4 sand core funnel.Fiber is added repeatedly
Deionized water centrifuge washing to neutrality, filtrate at 4000r/min is rotated under conditions of 60r/min at 70 DEG C, is obtained white
The citric acid crystalline solid of color.
(3) by the fiber after washing, by ultrasonic cell-break machine under conditions of 900W the every 5s of ultrasound 20min(
Have the interval of 5s after ultrasound), 200ml deionized water ultrasound 20min again is added after ultrasonic.
(4) after the centrifugation 10min that the cellulose suspension after ultrasound is passed through 4000r/min, cellulose nanometer is isolated
Brilliant (its atomic force microscopy diagram is shown in Fig. 1 a)；Remaining precipitating is diluted to 1wt%, prepares cellulose with high-pressure nano homogenizer
Nanofiber (its atomic force microscopy diagram is shown in Fig. 1 b).
(5) yield 32.2% of the prepared Cellulose nanocrystal of this experiment, surface-bound carboxylic content 0.6mmol/g, fiber
Plain nanofiber yield is 63.44%, surface-bound carboxylic content 0.3mmol/g, stands 30 days and does not precipitate.
Embodiment 2: the nano-cellulose of citric acid water solution combination ultrasonic wave added one-step preparation of carboxyl
(1) 100 DEG C at a temperature of, by the bleaching bagasse pulp plate of 5g over dry be added to concentration be 70wt% aqueous citric acid solution
4h is reacted in (70g citric acid, 30ml water), obtains hydrolysed suspension.
(2) hydrolysed suspension is filtered by vacuum to obtain solid fiber and filtrate by G4 sand core funnel.Fiber is added repeatedly
Deionized water centrifuge washing to neutrality, filtrate at 4000r/min is rotated under conditions of 60r/min at 70 DEG C, is obtained white
The citric acid crystalline solid of color.
(3) by the fiber after washing, by ultrasonic cell-break machine under conditions of 900W the every 5s of ultrasound 20min(
Have the interval of 5s after ultrasound), 200ml deionized water ultrasound 20min again is added after ultrasonic.
(4) after the centrifugation 10min that the cellulose suspension after ultrasound is passed through 4000r/min, cellulose nanometer is isolated
It is brilliant；Remaining precipitating is diluted to 1 wt%, is prepared with high-pressure nano homogenizer cellulose nano-fibrous.
(5) yield 26.17% of the prepared Cellulose nanocrystal of this experiment, surface-bound carboxylic content 0.4mmol/g, fiber
Plain nanofiber yield is 71.84%, surface-bound carboxylic content 0.2mmol/g, stands 30 days and does not precipitate.
Embodiment 3: the nano-cellulose of citric acid water solution combination ultrasonic wave added one-step preparation of carboxyl
(1) 100 DEG C at a temperature of, the bleached wood pulp pulpboard of 5g over dry is crushed to the citric acid water for being added to that concentration is 80wt%
4h is reacted in solution (80g citric acid, 20ml water), obtains hydrolysed suspension.
(2) hydrolysed suspension is filtered by vacuum to obtain solid fiber and filtrate by G4 sand core funnel.Fiber is added repeatedly
Deionized water centrifuge washing to neutrality, filtrate at 4000r/min is rotated under conditions of 60r/min at 70 DEG C, is obtained white
The citric acid crystalline solid of color.
(3) by the fiber after washing, by ultrasonic cell-break machine under conditions of 900W the every 5s of ultrasound 20min(
Have the interval of 5s after ultrasound), 200ml deionized water ultrasound 20min again is added after ultrasonic.
(4) after the centrifugation 10min that the cellulose suspension after ultrasound is passed through 4000r/min, cellulose nanometer is isolated
It is brilliant；Remaining precipitating is diluted to 1 wt%, is prepared with high-pressure nano homogenizer cellulose nano-fibrous.
(5) yield 31.26% of the prepared Cellulose nanocrystal of this experiment, surface-bound carboxylic content 0.65mmol/g are fine
Tieing up plain nanofiber yield is 70.67%, surface-bound carboxylic content 0.3mmol/g, stands 30 days and does not precipitate.
Embodiment 4: the nano-cellulose of citric acid water solution combination ultrasonic wave added one-step preparation of carboxyl
(1) 100 DEG C at a temperature of, the bleached wood pulp pulpboard of 5g over dry is crushed to the citric acid water for being added to that concentration is 70wt%
4h is reacted in solution (70g citric acid, 30ml water), obtains hydrolysed suspension.
(2) hydrolysed suspension is filtered by vacuum to obtain solid fiber and filtrate by G4 sand core funnel.Fiber is added repeatedly
Deionized water centrifuge washing to neutrality, filtrate at 4000r/min is rotated under conditions of 60r/min at 70 DEG C, is obtained white
The citric acid crystalline solid of color.
(3) by the fiber after washing, by ultrasonic cell-break machine under conditions of 900W the every 5s of ultrasound 20min(
Have the interval of 5s after ultrasound), 200ml deionized water ultrasound 20min again is added after ultrasonic.
(4) after the centrifugation 10min that the cellulose suspension after ultrasound is passed through 4000r/min, cellulose nanometer is isolated
It is brilliant；Remaining precipitating is diluted to 1 wt%, is prepared with high-pressure nano homogenizer cellulose nano-fibrous.
(5) yield 24.73% of the prepared Cellulose nanocrystal of this experiment, surface-bound carboxylic content 0.45mmol/g are fine
Tieing up plain nanofiber yield is 74.5%, surface-bound carboxylic content 0.25mmol/g, stands 30 days and does not precipitate.
Embodiment 5: the nano-cellulose of citric acid water solution combination ultrasonic wave added one-step preparation of carboxyl
(1) 100 DEG C at a temperature of, the bleaching straw pulp pulpboard of 5g over dry is crushed to the citric acid water for being added to that concentration is 80wt%
4h is reacted in solution (80g citric acid, 20ml water), obtains hydrolysed suspension.
(2) hydrolysed suspension is filtered by vacuum to obtain solid fiber and filtrate by G4 sand core funnel.Fiber is added repeatedly
Deionized water centrifuge washing to neutrality, filtrate at 4000r/min is rotated under conditions of 60r/min at 70 DEG C, is obtained white
The citric acid crystalline solid of color.
(3) by the fiber after washing, by ultrasonic cell-break machine under conditions of 900W the every 5s of ultrasound 20min(
Have the interval of 5s after ultrasound), 200ml deionized water ultrasound 20min again is added after ultrasonic.
(4) after the centrifugation 10min that the cellulose suspension after ultrasound is passed through 4000r/min, cellulose nanometer is isolated
It is brilliant；Remaining precipitating is diluted to 1 wt%, is prepared with high-pressure nano homogenizer cellulose nano-fibrous.
(5) yield 34.6% of the prepared Cellulose nanocrystal of this experiment, surface-bound carboxylic content 0.65mmol/g, fiber
Plain nanofiber yield is 64.53%, surface-bound carboxylic content 0.35mmol/g, stands 30 days and does not precipitate.
Embodiment 6: the nano-cellulose of citric acid water solution combination ultrasonic wave added one-step preparation of carboxyl
(1) 100 DEG C at a temperature of, the bleaching straw pulp pulpboard of 5g over dry is crushed to the citric acid water for being added to that concentration is 70wt%
4h is reacted in solution (70g citric acid, 30ml water), obtains hydrolysed suspension.
(2) hydrolysed suspension is filtered by vacuum to obtain solid fiber and filtrate by G4 sand core funnel.Fiber is added repeatedly
Deionized water centrifuge washing to neutrality, filtrate at 4000r/min is rotated under conditions of 60r/min at 70 DEG C, is obtained white
The citric acid crystalline solid of color.
(3) by the fiber after washing, by ultrasonic cell-break machine under conditions of 900W the every 5s of ultrasound 20min(
Have the interval of 5s after ultrasound), 200ml deionized water ultrasound 20min again is added after ultrasonic.
(4) after the centrifugation 10min that the cellulose suspension after ultrasound is passed through 4000r/min, cellulose nanometer is isolated
It is brilliant；Remaining precipitating is diluted to 1 wt%, is prepared with high-pressure nano homogenizer cellulose nano-fibrous.
(5) yield 25.67% of the prepared Cellulose nanocrystal of this experiment, surface-bound carboxylic content 0.4mmol/g, fiber
Plain nanofiber yield is 69.63%, surface-bound carboxylic content 0.25mmol/g, stands 30 days and does not precipitate.
Embodiment 7: the nano-cellulose of citric acid water solution combination ultrasonic wave added one-step preparation of carboxyl
(1) 100 DEG C at a temperature of, the bleached cotton starch pulpboard of 5g over dry is crushed to the citric acid water for being added to that concentration is 80wt%
2h is reacted in solution (80g citric acid, 20ml water), obtains hydrolysed suspension.
(2) hydrolysed suspension is filtered by vacuum to obtain solid fiber and filtrate by G4 sand core funnel.Fiber is added repeatedly
Deionized water centrifuge washing to neutrality, filtrate at 4000r/min is rotated under conditions of 60r/min at 70 DEG C, is obtained white
The citric acid crystalline solid of color.
(3) by the fiber after washing, by ultrasonic cell-break machine under conditions of 900W the every 5s of ultrasound 20min(
Have the interval of 5s after ultrasound), 200ml deionized water ultrasound 20min again is added after ultrasonic.
(4) after the centrifugation 10min that the cellulose suspension after ultrasound is passed through 4000r/min, cellulose nanometer is isolated
It is brilliant；Remaining precipitating is diluted to 1 wt%, is prepared with high-pressure nano homogenizer cellulose nano-fibrous.
(5) yield 20.81% of the prepared Cellulose nanocrystal of this experiment, surface-bound carboxylic content 0.3mmol/g, fiber
Plain nanofiber yield is 77.63%, surface-bound carboxylic content 0.15mmol/g, stands 30 days and does not precipitate.
Embodiment 8: the nano-cellulose of citric acid water solution combination ultrasonic wave added one-step preparation of carboxyl
(1) 100 DEG C at a temperature of, the bleached cotton starch pulpboard of 5g over dry is crushed to the citric acid water for being added to that concentration is 70wt%
2h is reacted in solution (70g citric acid, 30ml deionized water), obtains hydrolysed suspension.
(2) hydrolysed suspension is filtered by vacuum to obtain solid fiber and filtrate by G4 sand core funnel.Fiber is added repeatedly
Deionized water centrifuge washing to neutrality, filtrate at 4000r/min is rotated under conditions of 60r/min at 70 DEG C, is obtained white
The citric acid crystalline solid of color.
(3) by the fiber after washing, by ultrasonic cell-break machine under conditions of 900W the every 5s of ultrasound 20min(
Have the interval of 5s after ultrasound), 200ml deionized water ultrasound 20min again is added after ultrasonic.
(4) after the centrifugation 10min that the cellulose suspension after ultrasound is passed through 4000r/min, cellulose nanometer is isolated
It is brilliant；Remaining precipitating is diluted to 1 wt%, is prepared with high-pressure nano homogenizer cellulose nano-fibrous.
(5) yield 16.56% of the prepared Cellulose nanocrystal of this experiment, surface-bound carboxylic content 0.2mmol/g, fiber
Plain nanofiber yield is 81.63%, surface-bound carboxylic content 0.1mmol/g, stands 30 days and does not precipitate.
Embodiment 9: the nano-cellulose of citric acid water solution combination ultrasonic wave added one-step preparation of carboxyl
(1) 100 DEG C at a temperature of, the bleached bamboo pulp pulpboard of 5g over dry is crushed to the citric acid water for being added to that concentration is 80wt%
4h is reacted in solution (80g citric acid, 20ml deionized water), obtains hydrolysed suspension.
(2) hydrolysed suspension is filtered by vacuum to obtain solid fiber and filtrate by G4 sand core funnel.Fiber is added repeatedly
Deionized water centrifuge washing to neutrality, filtrate at 4000r/min is rotated under conditions of 60r/min at 70 DEG C, is obtained white
The citric acid crystalline solid of color.
(3) by the fiber after washing, by ultrasonic cell-break machine under conditions of 900W the every 5s of ultrasound 20min(
Have the interval of 5s after ultrasound), 200ml deionized water ultrasound 20min again is added after ultrasonic.
(4) after the centrifugation 10min that the cellulose suspension after ultrasound is passed through 4000r/min, cellulose nanometer is isolated
It is brilliant；Remaining precipitating is diluted to 1 wt%, is prepared with high-pressure nano homogenizer cellulose nano-fibrous.
(5) yield 36.56% of the prepared Cellulose nanocrystal of this experiment, surface-bound carboxylic content 0.65mmol/g are fine
Tieing up plain nanofiber yield is 61.44%, surface-bound carboxylic content 0.35mmol/g, stands 30 days and does not precipitate.
Embodiment 10: the nano-cellulose of citric acid water solution combination ultrasonic wave added one-step preparation of carboxyl
(1) 100 DEG C at a temperature of, the bleached bamboo pulp pulpboard of 5g over dry is crushed to the citric acid water for being added to that concentration is 70wt%
4h is reacted in solution (70g citric acid, 30ml water), obtains hydrolysed suspension.
(2) hydrolysed suspension is filtered by vacuum to obtain solid fiber and filtrate by G4 sand core funnel.Fiber is added repeatedly
Deionized water centrifuge washing to neutrality, filtrate at 4000r/min is rotated under conditions of 60r/min at 70 DEG C, is obtained white
The citric acid crystalline solid of color.
(3) by the fiber after washing, by ultrasonic cell-break machine under conditions of 900W the every 5s of ultrasound 20min(
Have the interval of 5s after ultrasound), 200ml deionized water ultrasound 20min again is added after ultrasonic.
(4) after the centrifugation 10min that the cellulose suspension after ultrasound is passed through 4000r/min, cellulose nanometer is isolated
It is brilliant；Remaining precipitating is diluted to 1 wt%, is prepared with high-pressure nano homogenizer cellulose nano-fibrous.
(5) yield 24.36% of the prepared Cellulose nanocrystal of this experiment, surface-bound carboxylic content 0.45mmol/g are fine
Tieing up plain nanofiber yield is 69.85%, surface-bound carboxylic content 0.25mmol/g, stands 30 days and does not precipitate.
Claims (10)
1. a kind of method hydrolyzed using citric acid and combine ultrasonic wave added preparation carboxylated nano-cellulose, which is characterized in that
Using bleached fiber pulpboard as substrate, is hydrolyzed by citric acid and the method for being aided with ultrasound prepares carboxylated nano-cellulose.
2. the method according to claim 1, wherein the carboxylated nano-cellulose includes cellulose nanometer
Brilliant and cellulose nanometer fibril.
3. the method according to claim 1, wherein the citric acid is aqueous citric acid solution.
4. the method according to claim 1, wherein the bleached fiber pulpboard is microcrystalline cellulose, bleaching sugarcane
One of slurry, bleached wood pulp, bleaching straw pulp, bleached cotton starch, bleached bamboo pulp or several mixed bleach pulpboards.
5. the method according to claim 1, wherein specifically comprising the following steps:
S1. citric acid is added to the water, forms aqueous citric acid solution after dissolution；
S2. over dry bleached fiber pulpboard is crushed, is added in aqueous citric acid solution and sufficiently reacts；
S3. reacted fibrous suspension is separated into fiber and filtrate by the method for vacuum filtration, with the method for revolving crystallization
Citric acid solid particle is recycled from filtrate；
S4. by the fiber isolated by be centrifuged method wash to neutrality, by ultrasound method by Cellulose nanocrystal most
It is detached from from fiber to bigization, then isolates Cellulose nanocrystal dispersion liquid with the method for centrifugation, by being freeze-dried or spraying
The Cellulose nanocrystal of solid is obtained after mist is dry；
S5. fibre solid precipitating remaining after the separation of Cellulose nanocrystal body is prepared by cellulose by high-pressure nano homogenizer
Nanofibrils obtain the cellulose nanometer fibril of solid after freeze-drying or spray drying.
6. according to the method described in claim 5, it is characterized in that, the concentration of aqueous citric acid solution described in step S1 is 60
wt%-80 wt%。
7. according to the method described in claim 5, it is characterized in that, the time of reaction described in step S2 be 0.5-4 hour, react
Temperature be 80 DEG C -120 DEG C.
8. according to the method described in claim 5, it is characterized in that, vacuum filtration G4 sand core funnel described in step S3.
9. according to the method described in claim 5, it is characterized in that, washing described in step S4 is that deionized water centrifugation is added repeatedly
To neutrality；The power of ultrasound is 600W-1200W, time 10-30min.
10. according to the method described in claim 5, it is characterized in that, high-pressure nano homogenizer described in step S5 is D8 high
Press reaction chamber, homogeneous 6-7 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811533245.5A CN109705226A (en) | 2018-12-14 | 2018-12-14 | A method of it is hydrolyzed using citric acid and ultrasonic wave added is combined to prepare carboxylated nano-cellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811533245.5A CN109705226A (en) | 2018-12-14 | 2018-12-14 | A method of it is hydrolyzed using citric acid and ultrasonic wave added is combined to prepare carboxylated nano-cellulose |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109705226A true CN109705226A (en) | 2019-05-03 |
Family
ID=66256443
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811533245.5A Pending CN109705226A (en) | 2018-12-14 | 2018-12-14 | A method of it is hydrolyzed using citric acid and ultrasonic wave added is combined to prepare carboxylated nano-cellulose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109705226A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110498949A (en) * | 2019-09-06 | 2019-11-26 | 天津科技大学 | A kind of preparation method of Cellulose nanocrystal body load silver nanoclusters composite material |
| CN110746655A (en) * | 2019-10-28 | 2020-02-04 | 上海工程技术大学 | pH sensitive nanosphere based on cellulose nanowhisker and preparation and application thereof |
| CN111019005A (en) * | 2019-12-13 | 2020-04-17 | 华南理工大学 | Method for preparing carboxylated nanocellulose by using citric acid hydrolysis and combining catalyst and ultrasonic-assisted two-step process |
| CN111072786A (en) * | 2019-12-13 | 2020-04-28 | 华南理工大学 | Method for preparing carboxylated nano-cellulose by hydrolyzing citric acid under high pressure condition |
| CN111087491A (en) * | 2019-12-13 | 2020-05-01 | 华南理工大学 | Method for preparing hemicellulose, carboxylated cellulose nano crystal, fibril and citrate multi-component product from fiber by using citric acid |
| CN111116763A (en) * | 2020-01-20 | 2020-05-08 | 天津科技大学 | Method for preparing cellulose nanocrystals by combining mechanical-assisted organic acid hydrolysis with ultrasound |
| CN111138555A (en) * | 2020-01-20 | 2020-05-12 | 天津科技大学 | Process for simultaneously preparing cellulose nanocrystals and cellulose nanofibrils |
| CN111944066A (en) * | 2019-05-14 | 2020-11-17 | 中国科学技术大学 | Cellulose-containing biomass material with nano-crystallized surface and preparation method and application thereof |
| CN113718543A (en) * | 2021-08-11 | 2021-11-30 | 华南理工大学 | Method for cleanly preparing cellulose nanocrystals by combining organic acid hydrolysis with nano-micro-jet homogenization one-step method and product |
| CN114277461A (en) * | 2021-12-24 | 2022-04-05 | 东北林业大学 | Carboxylated cellulose nano-fibril and preparation method thereof |
| CN114716572A (en) * | 2022-03-07 | 2022-07-08 | 浙江理工大学 | One-step preparation process of multi-functionalized nano-cellulose |
| CN115353568A (en) * | 2022-08-16 | 2022-11-18 | 河北农业大学 | Carboxylated cellulose nanocrystal, intelligent film, preparation method and application |
| SE2151623A1 (en) * | 2021-12-27 | 2023-06-28 | Finecell Sweden Ab | Process to manufacture acid hydrolysed celluloses |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646721A (en) * | 2016-01-21 | 2016-06-08 | 中国科学院青岛生物能源与过程研究所 | Preparation method of nanocellulose fibrils |
| CN106084071A (en) * | 2016-08-11 | 2016-11-09 | 中国科学院青岛生物能源与过程研究所 | A kind of method preparing nano-cellulose sustainably |
| US10066028B1 (en) * | 2017-05-11 | 2018-09-04 | King Saud University | Method of fabricating biocompatible cellulose nanofibrils |
-
2018
- 2018-12-14 CN CN201811533245.5A patent/CN109705226A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105646721A (en) * | 2016-01-21 | 2016-06-08 | 中国科学院青岛生物能源与过程研究所 | Preparation method of nanocellulose fibrils |
| CN106084071A (en) * | 2016-08-11 | 2016-11-09 | 中国科学院青岛生物能源与过程研究所 | A kind of method preparing nano-cellulose sustainably |
| US10066028B1 (en) * | 2017-05-11 | 2018-09-04 | King Saud University | Method of fabricating biocompatible cellulose nanofibrils |
Non-Patent Citations (2)
| Title |
|---|
| CHAO LIU等: "Simultaneous Extraction of Carboxylated Cellulose Nanocrystals and Nanofibrils via Citric Acid Hydrolysis—A Sustainable Route", 《CELLULOSE NANOCRYSTALS AND NANOFIBRILS》 * |
| 林雯怡: "机械力化学法制备纳米纤维素及其改性研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020228317A1 (en) * | 2019-05-14 | 2020-11-19 | 中国科学技术大学 | Cellulose-containing biomass material having surface nano-crystallization, preparation method therefor and use thereof |
| CN111944066A (en) * | 2019-05-14 | 2020-11-17 | 中国科学技术大学 | Cellulose-containing biomass material with nano-crystallized surface and preparation method and application thereof |
| CN110498949A (en) * | 2019-09-06 | 2019-11-26 | 天津科技大学 | A kind of preparation method of Cellulose nanocrystal body load silver nanoclusters composite material |
| CN110746655A (en) * | 2019-10-28 | 2020-02-04 | 上海工程技术大学 | pH sensitive nanosphere based on cellulose nanowhisker and preparation and application thereof |
| CN111087491A (en) * | 2019-12-13 | 2020-05-01 | 华南理工大学 | Method for preparing hemicellulose, carboxylated cellulose nano crystal, fibril and citrate multi-component product from fiber by using citric acid |
| CN111072786A (en) * | 2019-12-13 | 2020-04-28 | 华南理工大学 | Method for preparing carboxylated nano-cellulose by hydrolyzing citric acid under high pressure condition |
| CN111019005A (en) * | 2019-12-13 | 2020-04-17 | 华南理工大学 | Method for preparing carboxylated nanocellulose by using citric acid hydrolysis and combining catalyst and ultrasonic-assisted two-step process |
| CN111138555A (en) * | 2020-01-20 | 2020-05-12 | 天津科技大学 | Process for simultaneously preparing cellulose nanocrystals and cellulose nanofibrils |
| CN111116763A (en) * | 2020-01-20 | 2020-05-08 | 天津科技大学 | Method for preparing cellulose nanocrystals by combining mechanical-assisted organic acid hydrolysis with ultrasound |
| CN113718543A (en) * | 2021-08-11 | 2021-11-30 | 华南理工大学 | Method for cleanly preparing cellulose nanocrystals by combining organic acid hydrolysis with nano-micro-jet homogenization one-step method and product |
| CN114277461B (en) * | 2021-12-24 | 2023-01-13 | 东北林业大学 | Carboxylated cellulose nano-fibril and preparation method thereof |
| CN114277461A (en) * | 2021-12-24 | 2022-04-05 | 东北林业大学 | Carboxylated cellulose nano-fibril and preparation method thereof |
| SE2151623A1 (en) * | 2021-12-27 | 2023-06-28 | Finecell Sweden Ab | Process to manufacture acid hydrolysed celluloses |
| WO2023128851A1 (en) * | 2021-12-27 | 2023-07-06 | Finecell Sweden Ab | Process to manufacture acid hydrolysed celluloses |
| SE545910C2 (en) * | 2021-12-27 | 2024-03-12 | Finecell Ox Ab C/O Peter Axegaard | Process to manufacture acid hydrolysed celluloses |
| CN114716572A (en) * | 2022-03-07 | 2022-07-08 | 浙江理工大学 | One-step preparation process of multi-functionalized nano-cellulose |
| CN115353568A (en) * | 2022-08-16 | 2022-11-18 | 河北农业大学 | Carboxylated cellulose nanocrystal, intelligent film, preparation method and application |
| CN115353568B (en) * | 2022-08-16 | 2024-02-06 | 河北农业大学 | Carboxylated cellulose nanocrystalline, intelligent film, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109705226A (en) | A method of it is hydrolyzed using citric acid and ultrasonic wave added is combined to prepare carboxylated nano-cellulose | |
| CN103635628B (en) | The catalyzed conversion of biomass | |
| CN103866487B (en) | The preparation method of a kind of nano micro crystal cellulose/chitosan/polyvinyl alcohol composite nanometer film | |
| AU2011284253B2 (en) | Method for production of cellulose nano crystals from cellulose-containing waste materials | |
| CN103061174B (en) | The method preparing cellulose nanometer fibril is assisted in a kind of strong acid preliminary treatment | |
| CN108659135B (en) | Preparation method of cellulose nanofiber or chitin nanofiber dispersion liquid | |
| CN105646721A (en) | Preparation method of nanocellulose fibrils | |
| CN111087491B (en) | Method for preparing hemicellulose, carboxylated cellulose nano crystal, fibril and citrate multi-component product from fiber by using citric acid | |
| CN105568730A (en) | Method for preparing renewable nano-celluloses | |
| CN103060937A (en) | Preparation method of cellulose nanofiber | |
| CN113718543A (en) | Method for cleanly preparing cellulose nanocrystals by combining organic acid hydrolysis with nano-micro-jet homogenization one-step method and product | |
| CN107236049A (en) | A kind of nano-cellulose and preparation method thereof | |
| CN107602709B (en) | Clean preparation method of carboxymethyl nano-cellulose material | |
| CN106149433B (en) | Nano-cellulose and preparation method thereof | |
| CN102817276A (en) | Method for preparing cellulose nano-grade filament film by using recovered waste paper | |
| CN106988137A (en) | A kind of clean preparation method of higher concentration nano-cellulose fibril | |
| CN108221438A (en) | A kind of preparation method of bleached eucalyptus pulp nano-cellulose | |
| CN102093484A (en) | Method for preparing nano crystal cellulose by dissociating ZnCl2 | |
| CN108252136A (en) | A kind of preparation method of the wooden nanofiber of wheat stalk | |
| CN108457112A (en) | A method of preparing nano-cellulose whisker and fibril using oxalic acid acidolysis | |
| CN107474343A (en) | The method that one kettle way prepares ascidian nano micro crystal cellulose/rubber nano composite material | |
| CN111019005A (en) | Method for preparing carboxylated nanocellulose by using citric acid hydrolysis and combining catalyst and ultrasonic-assisted two-step process | |
| CN114197233B (en) | Method for separating and extracting cellulose nanofibers from agricultural and forestry solid wastes | |
| Jančíková et al. | The role of deep eutectic solvents in the production of cellulose nanomaterials from biomass | |
| CN111072786A (en) | Method for preparing carboxylated nano-cellulose by hydrolyzing citric acid under high pressure condition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |