CN108219008A - Nano cellulose crystal and method prepared by acid hydrolyzed cellulose microfibril - Google Patents
Nano cellulose crystal and method prepared by acid hydrolyzed cellulose microfibril Download PDFInfo
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Abstract
The nano cellulose crystal and method prepared the present invention relates to a kind of acid hydrolyzed cellulose microfibril first takes slurry defibrination that pretreatment, isolated fiber after hydrolysis pretreatment are hydrolyzed again；Obtained fiber is configured to fibrous suspension, carries out high-pressure homogeneous processing and drying, obtains cellulose microfibril；Cellulose microfibril is taken to be configured to the microfibril suspension that mass concentration is 1%~2% with acid solution, is reacted 5~8 hours at 30 DEG C~45 DEG C；After reaction, obtained mixed liquor is subjected to dialysis until neutral, is then evaporated to thick, be dried to obtain nano cellulose crystal.The present invention prepares nano cellulose crystal using pretreatment with reference to mechanical dissociation assist acid hydrolysis, reduces the generation of wastewater from chemical industry, reduces production cost and carrying capacity of environment；The efficiency that sour water solution destroys fiber finer cell wall is improved, increases reaction rate, improves yield, saves energy consumption.
Description
Technical field
The invention belongs to the fields of nano material, and in particular to nanofiber prepared by a kind of acid hydrolyzed cellulose microfibril
Cellulose crystal and method.
Background technology
Usual nano cellulose crystal (nanocrystalline cellulose, NCC) refers at least one-dimensional space size
In the cellulose of 1~100nm.Compared with native cellulose and microcrystalline cellulose, it has larger specific surface area, highly crystalline
The excellent performances such as degree, high-hydrophilic, high-modulus, high intensity, hyperfine structure and high transparency.Therefore it is in fine chemistry industry, multiple
Condensation material, medical carrier, medicament slow release etc. have broad application prospects.The side of the common preparation of nano cellulose crystal
Method is mineral acid hydrolysis method, and most common inorganic acid is sulfuric acid.In addition to this, also phosphoric acid and hydrochloric acid, also someone by sulfuric acid and
Hydrochloric acid is mixed in a certain ratio use.But simple strong acid treatment can generate a large amount of spent acid and impurity, preparation process takes
It is more, step is more, high energy consumption, a large amount of water resource of consumption, equipment requirement is high.Mineral acid hydrolysis preparation is received therefore, it is necessary to a kind of
The method that the process of rice cellulose crystals optimizes.
Invention content
It is an object of the invention to overcome problems of the prior art, a kind of acid hydrolyzed cellulose microfibril system is provided
Standby nano cellulose crystal and method can reduce the generation of wastewater from chemical industry, improve efficiency.
In order to achieve the above object, the present invention adopts the following technical scheme that：
Include the following steps：
(1) take slurry defibrination that pretreatment, isolated fiber after hydrolysis pretreatment are hydrolyzed again；
(2) fiber that step (1) obtains is configured to fibrous suspension, carries out high-pressure homogeneous processing and drying, obtained fine
The plain microfibril of dimension；
(3) cellulose microfibril is taken to be configured to the microfibril suspension that mass concentration is 1%~2% with acid solution, 30
DEG C~45 DEG C at react 5~8 hours；
(4) obtained mixed liquor after reaction, is carried out dialysis until neutrality, is then evaporated to sticky by step (3)
Shape is dried to obtain nano cellulose crystal.
Further, in step (1), slurry is using bleaching needle-point leaf pulp over dry pulp or bleached softwood wood-fibred over dry
What pulp was formulated with water, slurry concentration is 10%~15%.
Further, in step (1), the time of defibrination is 15min~20min.
Further, in step (1), hydrolysis pretreatment is to carry out sour water solution, enzyme hydrolysis or oxygen to the slurry after defibrination
Change hydrolysis；Wherein,
Sour water solution includes the following steps：First the slurry after defibrination and sulfuric acid are mixed, are configured to a concentration of 2%~4%
Fibrous suspension reacts 20~50min at 40 DEG C~50 DEG C, terminates filtration washing after reaction, collects fiber；
Enzyme hydrolysis includes the following steps：Slurry after cellulase and defibrination is added to the sodium citrate that pH value is 4~5
In buffer solution, a concentration of 2%~3% fibrous suspension is configured to, in 50 DEG C~55 DEG C oscillating reactions 2~3 hours, reaction
After by inactivation and filtering, collect fiber；
Oxydrolysis includes the following steps：Slurry with water after defibrination is configured to a concentration of 1%~2% fiber suspension
Then liquid adds in TEMPO solution, sodium bromide and liquor natrii hypochloritis into fibrous suspension, react 1~2 hour, crosses diafiltration
It washs, collects fiber；Wherein, the mass ratio of bone dry fiber in fibrous suspension, TEMPO, sodium bromide and sodium hypochlorite is (1~2)：
0.11g：0.32g：1.5g；A concentration of 0.11g/mL of TEMPO solution, a concentration of 0.5g/mL of liquor natrii hypochloritis.
Further, in step (2), a concentration of the 1~1.5% of fibrous suspension.
Further, in step (2), the number of homogenization is 10~20 times, and homogenization pressure is 100MPa~150MPa.
Further, in step (2), drying is to be freeze-dried 12h~for 24 hours at -10 DEG C~-50 DEG C.
Further, in step (3), acid solution is using the sulfuric acid that volume fraction is 40%~50%.
Further, in step (4), drying is that freeze-drying 12~for 24 hours is carried out at -10 DEG C~-50 DEG C.
It is a kind of to utilize nano cellulose crystal made from method as described above, it is characterised in that：The nano cellulose crystal
For club shaped structure or chondritic, average grain diameter is in 30nm~70nm.
Compared with prior art, the present invention has technique effect beneficial below：
First, a large amount of impurity and spent acid phase can be generated during nano cellulose crystal is prepared with traditional inorganic acid
Than the present invention prepares nano cellulose crystal using pretreatment with reference to mechanical dissociation assist acid hydrolysis, reduces the production of wastewater from chemical industry
It is raw, reduce production cost and carrying capacity of environment；
2nd, the present invention first prepares nano cellulose crystal using pretreatment with reference to mechanical dissociation assist acid hydrolysis, significantly
The efficiency that sour water solution destroys fiber finer cell wall is improved, increases reaction rate, improves yield, yield can reach 60~
80%, save energy consumption；
3rd, compared with traditional sulphuric acid hydrolysis prepares nano cellulose crystal, the mild condition of sour water solution use in the present invention,
Temperature is relatively low, and preparation method is simple, and the nano cellulose crystal prepared by this method can reach requirement.
Description of the drawings
Fig. 1 is the SEM figures of NCC prepared by 1 low-kappa number of embodiment.
Fig. 2 is the SEM figures that 2 enzyme pretreatment of embodiment prepares NCC.
Fig. 3 is the SEM figures that embodiment 3TEMPO oxidation pre-treatments prepare NCC.
Specific embodiment
The present invention is described in further details below in conjunction with the accompanying drawings.
The processing of mechanical dissociation assistant chemical is combined the present invention provides a kind of pretreatment, biological treatment prepares nano-cellulose
The method of crystal, and prepare spherical and club shaped structure nano cellulose crystal.Specific preparation method is as follows：
(1) by the slurry that mass concentration is 10%~15%, with PFI paste mill grinding 15min~20min, slurry is obtained
I；Wherein, the fiber of slurry uses bleaching needle-point leaf pulp over dry pulp or bleached softwood wood-fibred over dry pulp；
(2) slurry I sulfuric acid, cellulase or 2,2,6,6- tetramethyl piperidines nitrogen oxides (TEMPO) is taken to be located in advance
Reason；
Sour water solution carries out in thermostat water bath, and slurry I and volume fraction 40% are separately added into round-bottomed flask
~50% sulfuric acid is configured to a concentration of 2%~4% fibrous suspension, and 20~50min is reacted at 40 DEG C~50 DEG C, and
It is stirred continuously.Reaction is terminated with 20~30 times of distilled water after reaction, then with filtered on buchner funnel, distills and washs repeatedly,
Fiber is collected when filtrate is in neutrality.
Cellulase is complex cellulase, exocellulase or endo cellulase；Wherein, it is multiple in step (2)
The enzyme dosage of condensating fiber element enzyme and exocellulase is used in 5FPU/g~10FPU/g bone dry fibers, the enzyme of endo cellulase
Amount is in 20CMCU/g~60CMCU/g bone dry fibers.Enzyme hydrolysis is that slurry I and cellulase are added in the lemon that pH value is 4~5
In sour sodium buffer solution, be configured to 2%~3% fibrous suspension, in 50~55 DEG C of thermostatic control oscillator vibration react 2~
3 hours, hunting speed was 70r/min~120r/min, inactivates 10~15min with boiling water bath after reaction；Then it filters simultaneously
Collect fiber.Wherein, cellulase can also be added in first in the sodium citrate buffer that pH value is 4~5 and be dissolved, and then be added again
Enter slurry I.
The condition of TEMPO oxidation pre-treatments is：Slurry I is configured to water to 1~2% fibrous suspension, first fully
Addition 0.11g TEMPO (solution 1ml), the stirring of 0.32g sodium bromides make it fully dissolve after stirring a period of time, then a small amount of more
Secondary addition 1.5g sodium hypochlorite (solution 3ml), is stirred to react, and ensures that total reaction time at 1~2 hour, is finally filtered and is used in combination
Distilled water collects fiber after washing repeatedly.
(3) fiber that step (2) obtains is configured to a concentration of 1~1.5% fibrous suspension, then by fiber suspension
Liquid carries out high-pressure homogeneous processing by high pressure homogenizer, and the number of homogenization is 10~20 times, homogenization pressure for 100MPa~
150MPa is finally freeze-dried 12h~for 24 hours at -10 DEG C~-50 DEG C, obtains cellulose microfibril；Wherein, preferred cycle 10 times,
It is preferred that pressure is 100MPa；
(4) obtained cellulose microfibril in a certain amount of step (3) is weighed, with the sulphur that volume fraction is 40~50%
Acid is configured to the suspension that mass concentration is 1~2%, is then reacted 5~8 hours at 30~45 DEG C, and when reaction is stirred continuously,
Mixing speed is 30r/min；
(5) mixed liquor that step (4) obtains is poured into bag filter and dialysed, until pH value reaches neutral；
(6) mixed liquor for obtaining step (5) is evaporated to thick with Rotary Evaporators, then -10 DEG C~-50 DEG C into
Row freeze-drying 12~for 24 hours, obtain nano cellulose crystal.
It is mass concentration wherein to starch dense.
Embodiment 1
A concentration of 10% bleaching needle-point leaf pulp PFI fiberizers are handled into 15min.Weigh the slurry after 3g (over dry) defibrination
Material (while the another slurry that weighs measures moisture) is fitted into round-bottomed flask, adds in 50% sulfuric acid, it is 3% to adjust slurry concentration.It will circle
Bottom flask is placed in thermostat water bath, and set temperature is 45 DEG C, reacts 30min, and be stirred continuously, after reaction burns round bottom
Bottle takes out, and the distilled water for adding in 30 times terminates reaction.Then with filtered on buchner funnel, distilled water, which is washed repeatedly to filtrate, is not in
Until acidity, fiber and equilibrium water conten are collected.The fiber 1g (over dry) after sour water solution is taken, a concentration of 1% fiber is configured to and hangs
Then supernatant liquid is handled 10 times, homogenization pressure 100MPa with high pressure homogenizer.Centrifuged suspension collects solid content, at -40 DEG C
Under, obtain cellulose microfibril after being freeze-dried 12h.Cellulose microfibril 2g (over dry) is taken, is adjusted with 50% sulfuric acid to dense
It is 1% to spend, and is reacted 8 hours in 45 DEG C of water-bath, mixing speed 30r/min.Mixed liquor after reaction is shifted
It dialyses into bag filter, until pH value is neutrality, Rotary Evaporators is recycled to be evaporated to neutral mixed liquor thick ,-
At 40 DEG C, freeze-drying obtains nano cellulose crystal for 24 hours.
As shown in Figure 1, obtained nano cellulose crystal：Club shaped structure, average grain diameter 30nm, yield 60%.
Embodiment 2
A concentration of 10% bleaching needle-point leaf pulp material PFI fiberizers are handled into 15min.After weighing 3g (over dry) defibrination
Slurry (while the another slurry that weighs measures moisture) is fitted into conical flask, is added in the complex cellulase of 5FPU/g bone dry fibers, is used
The citrate buffer solution of pH=4.8 is configured to a concentration of 3% cellulose suspension.Conical flask is placed in 50 DEG C of water bath with thermostatic control
It is reacted 2 hours in oscillator, conical flask is placed in boiling water bath inactivates after reaction by hunting speed 70r/min immediately
10min.With filtered on buchner funnel, distilled water washs repeatedly, collects fiber and equilibrium water conten.Take the fiber 1g after enzyme hydrolysis (absolutely
It is dry), be configured to a concentration of 1% fibrous suspension, then handled 10 times with high pressure homogenizer, homogenization pressure 100MPa.From
Suspension, collects solid content, and -40 DEG C of freeze-drying 12h obtain cellulose microfibril.Cellulose microfibril 2g (over dry) is taken,
It is adjusted to a concentration of 1%, is reacted 8 hours in 45 DEG C of water-bath, mixing speed 30r/min with 50% sulfuric acid.Reaction
After mixed liquor be transferred in bag filter and dialyse, until pH value is neutrality, recycle Rotary Evaporators by neutral mixing
Liquid be evaporated to it is thick, through -40 DEG C freeze-drying 12h obtain nano cellulose crystal.
As shown in Fig. 2, obtained nano cellulose crystal：Chondritic, average grain diameter 40nm, yield 65%.
Embodiment 3
A concentration of 10% bleaching needle-point leaf pulp material PFI fiberizers are handled into 15min.After weighing 3g (over dry) defibrination
Slurry (while the another slurry that weighs measures moisture) is fitted into conical flask, and a concentration of 1% slurry is configured to distilled water, is constantly stirred
It mixes so that slurry is fully dispersed.0.11g TEMPO (solution 1ml) are added in, 0.32g sodium bromides, being stirred continuously makes it fully dissolve,
1.50g sodium hypochlorite (solution 3ml) (a small amount of repeatedly to add in) is added in 30min, is stirred 1 hour.With filtered on buchner funnel, steam
Distilled water is washed repeatedly, collects fiber and equilibrium water conten.TEMPO is taken treated fiber 1g (over dry), be configured to a concentration of 1%
Then fibrous suspension is handled 10 times, homogenization pressure 100MPa with high pressure homogenizer.Centrifuged suspension collects solid content ,-
40 DEG C of freeze-drying 12h obtain cellulose microfibril.Cellulose microfibril 2g (over dry) is taken, is adjusted with 50% sulfuric acid to concentration
It is 1%, is reacted 8 hours in 45 DEG C of water-bath, mixing speed 30r/min.Mixed liquor after reaction is transferred to
It dialyses in analysis bag, until pH value is neutrality, Rotary Evaporators is recycled to be evaporated to neutral mixed liquor thick, through -40 DEG C
Freeze-drying 12h obtains nano cellulose crystal.
As shown in figure 3, obtained nano cellulose crystal：Chondritic, average grain diameter 70nm, yield 80%.
Comparative example 1 (non-acid pretreatment and high-pressure homogeneous processing, other conditions are with embodiment 1)
A concentration of 10% bleaching needle-point leaf pulp PFI fiberizers are handled into 15min.Weigh the slurry after 3g (over dry) defibrination
Material (while the another slurry that weighs measures moisture) is fitted into round-bottomed flask, adds in 50% sulfuric acid, it is 3% to adjust slurry concentration.It will circle
Bottom flask is placed in water-bath, and set temperature is 45 DEG C, rotating speed 30r/min, and after reacting 8 hours, mixed liquor is poured into dialysis
It dialyses in bag, until the pH value of mixed liquor is neutrality.Neutral mixed liquor is carrying out high speed centrifugation, and supernatant is with Rotary Evaporators
Processing is obtaining nano cellulose crystal in 12 hours to thick by freeze-drying.
Obtained nano cellulose crystal：Chondritic, average grain diameter 210nm, yield 40%.
Comparative example 2 (no pretreatment, other conditions are with embodiment 1)
A concentration of 10% bleaching needle-point leaf pulp material PFI fiberizers are handled into 15min.After weighing 1g (over dry) defibrination
Slurry (while the another slurry that weighs measures moisture), it is 1% to adjust slurry concentration with distilled water.It is handled 10 times with high pressure homogenizer,
Homogenization pressure is 100MPa, is centrifuged, and collects solid content, freeze-drying.The fiber 2g (over dry) after freeze-drying is taken, is used
50% sulfuric acid is adjusted to a concentration of 1%, is reacted 8 hours in 45 DEG C of water-bath, mixing speed 30r/min.It will reaction
After mixed liquor be transferred in bag filter and dialyse, until pH value is neutrality, recycle Rotary Evaporators by neutral mixing
Liquid is evaporated to thick, and freeze-dried 12h obtains nano cellulose crystal
Obtained nano cellulose crystal：Chondritic, average grain diameter 140nm, yield 50%.
By embodiment 1 and comparative example 1 and 2 as can be seen that the application effectively raises the yield of NCC, gained production
Object average grain diameter smaller.
By compared with other preparation methods, as Wang Haiying et al. has been inquired into using Eucalyptus paddle as raw material, using sulfuric acid process
The optimised process for preparing NCC is that sulfuric acid concentration is 55%, and temperature is 52 DEG C, and the time is 4 hours.Wang Zhi flies et al. using bamboo pulp as original
Material, optimizes its technological parameter using response surface optimization method, the results showed that the optimised process for preparing NCC is sulfuric acid concentration 60%, warm
53 DEG C of degree hydrolyzes 128min, and yield is 55.28% at this time.The application reduces the concentration and temperature that sulfuric acid uses, and improves
Rate.
Embodiment 4
A concentration of 12% bleached softwood wood-fibred slurry PFI fiberizers are handled into 18min.After weighing 2g (over dry) defibrination
Slurry (while the another slurry that weighs measures moisture) is fitted into round-bottomed flask, add in 40% sulfuric acid, it is 2% to adjust slurry concentration.
Round-bottomed flask is placed in thermostat water bath, set temperature is 40 DEG C, reacts 50min, and be stirred continuously, after reaction will circle
Bottom flask takes out, and the distilled water for adding in 20 times terminates reaction.Then filtered on buchner funnel is used, distilled water is washed repeatedly to filtrate
Until not in acidity, fiber and equilibrium water conten are collected.The fiber 1.2g (over dry) after sour water solution is taken, is configured to a concentration of 1.2%
Fibrous suspension, then with high pressure homogenizer handle 15 times, homogenization pressure 150MPa.Centrifuged suspension collects solid content,
At -10 DEG C, freeze-drying obtains cellulose microfibril afterwards for 24 hours.Cellulose microfibril 1.5g (over dry) is taken, with 40% sulfuric acid
It adjusts to a concentration of 1.5%, is reacted 7 hours in 30 DEG C of water-bath, mixing speed 30r/min.It will after reaction
Mixed liquor is transferred in bag filter and dialyses, until pH value is neutrality, Rotary Evaporators is recycled to be evaporated to neutral mixed liquor
Thick, at -10 DEG C, freeze-drying obtains nano cellulose crystal for 24 hours.
Embodiment 5
A concentration of 15% bleached softwood wood-fibred slurry PFI fiberizers are handled into 20min.After weighing 4g (over dry) defibrination
Slurry (while the another slurry that weighs measures moisture) is fitted into round-bottomed flask, add in 45% sulfuric acid, it is 4% to adjust slurry concentration.
Round-bottomed flask is placed in thermostat water bath, set temperature is 50 DEG C, reacts 20min, and be stirred continuously, after reaction will circle
Bottom flask takes out, and the distilled water for adding in 25 times terminates reaction.Then filtered on buchner funnel is used, distilled water is washed repeatedly to filtrate
Until not in acidity, fiber and equilibrium water conten are collected.The fiber 1.5g (over dry) after sour water solution is taken, is configured to a concentration of 1.5%
Fibrous suspension, then with high pressure homogenizer handle 20 times, homogenization pressure 120MPa.Centrifuged suspension collects solid content,
At -50 DEG C, cellulose microfibril is obtained after being freeze-dried 14h.Cellulose microfibril 2g (over dry) is taken, with 45% sulfuric acid tune
Section reacts 5 hours, mixing speed 30r/min to a concentration of 2% in 40 DEG C of water-bath.By mixing after reaction
Liquid is transferred in bag filter and dialyses, until pH value is neutrality, Rotary Evaporators is recycled to be evaporated to neutral mixed liquor sticky
Shape, at -50 DEG C, freeze-drying 14h obtains nano cellulose crystal.
Embodiment 6
A concentration of 10% bleaching needle-point leaf pulp material PFI fiberizers are handled into 15min.After weighing 2g (over dry) defibrination
Slurry (while the another slurry that weighs measures moisture) is fitted into conical flask, is added in the exocellulase of 10FPU/g bone dry fibers, is used
The citrate buffer solution of pH=4 is configured to a concentration of 2% cellulose suspension.Conical flask is placed in 52 DEG C of water bath with thermostatic control to shake
It swings in device and reacts 3 hours, conical flask is placed in boiling water bath inactivates 12min after reaction by hunting speed 100r/min immediately.
With filtered on buchner funnel, distilled water washs repeatedly, collects fiber and equilibrium water conten.The fiber 1.1g (over dry) after enzyme hydrolysis is taken,
A concentration of 1.1% fibrous suspension is configured to, is then handled 12 times with high pressure homogenizer, homogenization pressure 110MPa.Centrifugation
Suspension, collects solid content, and -20 DEG C of freeze-drying 20h obtain cellulose microfibril.Cellulose microfibril 1.2g (over dry) is taken,
It is adjusted to a concentration of 1.2%, is reacted 6 hours in 35 DEG C of water-bath, mixing speed 30r/min with 45% sulfuric acid.Instead
Mixed liquor after answering, which is transferred in bag filter, dialyses, until pH value is neutrality, recycles Rotary Evaporators by the mixed of neutrality
Close liquid be evaporated to it is thick, through -20 DEG C freeze-drying 20h obtain nano cellulose crystal.
Embodiment 7
A concentration of 10% bleaching needle-point leaf pulp material PFI fiberizers are handled into 15min.After weighing 2.5g (over dry) defibrination
Slurry (while the another slurry that weighs measures moisture) is fitted into conical flask, the inscribe cellulose of addition 40CMCU/g bone dry fibers
Enzyme is configured to a concentration of 2.5% cellulose suspension with the citrate buffer solution of pH=5.Conical flask is placed in 55 DEG C of perseverance
It is reacted 2.5 hours in tepidarium oscillator, conical flask is placed in boiling water bath by hunting speed 120r/min immediately after reaction
Inactivate 15min.With filtered on buchner funnel, distilled water washs repeatedly, collects fiber and equilibrium water conten.Take the fiber after enzyme hydrolysis
1.4g (over dry) is configured to a concentration of 1.4% fibrous suspension, is then handled 14 times with high pressure homogenizer, and homogenization pressure is
130MPa.Centrifuged suspension, collects solid content, and -30 DEG C of freeze-drying 15h obtain cellulose microfibril.Take cellulose microfibril
1.4g (over dry) is adjusted with 45% sulfuric acid to a concentration of 1.4%, is reacted 5.5 hours in 38 DEG C of water-bath, mixing speed
For 30r/min.Mixed liquor after reaction, which is transferred in bag filter, dialyses, until pH value is neutrality, recycles rotary evaporation
Neutral mixed liquor is evaporated to thick by instrument, and nano cellulose crystal is obtained through -30 DEG C of freeze-drying 15h.
Embodiment 8
A concentration of 10% bleaching needle-point leaf pulp material PFI fiberizers are handled into 15min.After weighing 1.5g (over dry) defibrination
Slurry (while the another slurry that weighs measures moisture) be fitted into conical flask, a concentration of 1.5% slurry is configured to distilled water, no
Disconnected stirring is so that slurry is fully dispersed.0.11g TEMPO (solution 1ml) are added in, 0.32g sodium bromides, being stirred continuously makes it fully
Dissolving adds in 1.50g sodium hypochlorite (solution 3ml) (a small amount of repeatedly to add in) in 30min, stirs 1.5 hours.Use Buchner funnel
Filtering, distilled water wash repeatedly, collect fiber and equilibrium water conten.TEMPO is taken treated fiber 1.3g (over dry), be configured to dense
The fibrous suspension for 1.3% is spent, is then handled 18 times with high pressure homogenizer, homogenization pressure 140MPa.Centrifuged suspension is received
Collect solid content, -35 DEG C of freeze-drying 13h obtain cellulose microfibril.Cellulose microfibril 1.6g (over dry) is taken, with 45% sulphur
Acid is adjusted to a concentration of 1.6%, is reacted 6 hours in 35 DEG C of water-bath, mixing speed 30r/min.After reaction
Mixed liquor is transferred in bag filter and dialyses, until pH value is neutrality, Rotary Evaporators is recycled to be evaporated to neutral mixed liquor
It is thick, obtain nano cellulose crystal through -35 DEG C of freeze-drying 13h.
Embodiment 9
A concentration of 10% bleaching needle-point leaf pulp material PFI fiberizers are handled into 15min.After weighing 2g (over dry) defibrination
Slurry (while the another slurry that weighs measures moisture) is fitted into conical flask, and a concentration of 2% slurry is configured to distilled water, is constantly stirred
It mixes so that slurry is fully dispersed.0.11g TEMPO (solution 1ml) are added in, 0.32g sodium bromides, being stirred continuously makes it fully dissolve,
1.50g sodium hypochlorite (solution 3ml) (a small amount of repeatedly to add in) is added in 30min, is stirred 2 hours.With filtered on buchner funnel, steam
Distilled water is washed repeatedly, collects fiber and equilibrium water conten.TEMPO is taken treated fiber 1.5g (over dry), be configured to a concentration of
Then 1.5% fibrous suspension is handled 16 times, homogenization pressure 135MPa with high pressure homogenizer.Centrifuged suspension is collected solid
Shape object, -45 DEG C of freeze-drying 12h obtain cellulose microfibril.Cellulose microfibril 1.8g (over dry) is taken, with 45% sulfuric acid tune
Section reacts 5.5 hours, mixing speed 30r/min to a concentration of 1.8% in 38 DEG C of water-bath.After reaction mixed
Conjunction liquid, which is transferred in bag filter, dialyses, until pH value is neutrality, Rotary Evaporators is recycled to be evaporated to the mixed liquor of neutrality viscous
Thick shape obtains nano cellulose crystal through -45 DEG C of freeze-drying 12h.
Claims (10)
1. a kind of method that acid hydrolyzed cellulose microfibril prepares nano cellulose crystal, it is characterised in that：Include the following steps：
(1) take slurry defibrination that pretreatment, isolated fiber after hydrolysis pretreatment are hydrolyzed again；
(2) fiber that step (1) obtains is configured to fibrous suspension, carries out high-pressure homogeneous processing and drying, obtain cellulose
Microfibril；
(3) take cellulose microfibril with acid solution be configured to mass concentration be 1%~2% microfibril suspension, 30 DEG C~
It is reacted 5~8 hours at 45 DEG C；
(4) obtained mixed liquor after reaction, is carried out dialysis until neutral by step (3), is then evaporated to thick, is done
It is dry to obtain nano cellulose crystal.
2. the method that a kind of acid hydrolyzed cellulose microfibril according to claim 1 prepares nano cellulose crystal, special
Sign is：In step (1), slurry is to be matched using bleaching needle-point leaf pulp over dry pulp or bleached softwood wood-fibred over dry pulp with water
What system formed, slurry concentration is 10%~15%.
3. the method that a kind of acid hydrolyzed cellulose microfibril according to claim 1 prepares nano cellulose crystal, special
Sign is：In step (1), the time of defibrination is 15min~20min.
4. the method that a kind of acid hydrolyzed cellulose microfibril according to claim 1 prepares nano cellulose crystal, special
Sign is：In step (1), hydrolysis pretreatment is to carry out sour water solution, enzyme hydrolysis or oxydrolysis to the slurry after defibrination；Its
In, sour water solution includes the following steps：First the slurry after defibrination and sulfuric acid are mixed, a concentration of 2%~4% fiber is configured to and hangs
Supernatant liquid reacts 20~50min at 40 DEG C~50 DEG C, terminates filtration washing after reaction, collects fiber；
Enzyme hydrolysis includes the following steps：Slurry after cellulase and defibrination is added to the buffered sodium citrate that pH value is 4~5
In solution, a concentration of 2%~3% fibrous suspension is configured to, in 50 DEG C~55 DEG C oscillating reactions 2~3 hours, reaction terminated
Afterwards by inactivating and filtering, fiber is collected；
Oxydrolysis includes the following steps：Slurry with water after defibrination is configured to a concentration of 1%~2% fibrous suspension,
Then TEMPO solution, sodium bromide and liquor natrii hypochloritis are added in into fibrous suspension, is reacted 1~2 hour, filtration washing, is received
Collect fiber；Wherein, the mass ratio of bone dry fiber in fibrous suspension, TEMPO, sodium bromide and sodium hypochlorite is (1~2)：
0.11g：0.32g：1.5g；A concentration of 0.11g/mL of TEMPO solution, a concentration of 0.5g/mL of liquor natrii hypochloritis.
5. the method that a kind of acid hydrolyzed cellulose microfibril according to claim 1 prepares nano cellulose crystal, special
Sign is：In step (2), a concentration of the 1~1.5% of fibrous suspension.
6. the method that a kind of acid hydrolyzed cellulose microfibril according to claim 1 prepares nano cellulose crystal, special
Sign is：In step (2), the number of homogenization is 10~20 times, and homogenization pressure is 100MPa~150MPa.
7. the method that a kind of acid hydrolyzed cellulose microfibril according to claim 1 prepares nano cellulose crystal, special
Sign is：In step (2), drying is to be freeze-dried 12h~for 24 hours at -10 DEG C~-50 DEG C.
8. the method that a kind of acid hydrolyzed cellulose microfibril according to claim 1 prepares nano cellulose crystal, special
Sign is：In step (3), acid solution is using the sulfuric acid that volume fraction is 40%~50%.
9. the method that a kind of acid hydrolyzed cellulose microfibril according to claim 1 prepares nano cellulose crystal, special
Sign is：In step (4), drying is that freeze-drying 12~for 24 hours is carried out at -10 DEG C~-50 DEG C.
10. a kind of utilize nano cellulose crystal made from claim 1 the method, it is characterised in that：The nano-cellulose
Crystal is club shaped structure or chondritic, and average grain diameter is in 30nm~70nm.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109096546A (en) * | 2018-07-27 | 2018-12-28 | 上海理工大学 | A method of high performance plastic film is produced using Cellulose nanocrystal body |
| CN109320616A (en) * | 2018-08-17 | 2019-02-12 | 东莞理工学院 | A kind of nano-cellulose and preparation method thereof of metal salt catalyst formic acid hydrolysis preparation |
| CN112725917A (en) * | 2020-12-28 | 2021-04-30 | 海南华创槟榔研究院 | Preparation method of areca seed cellulose nanofibrils |
| CN113123159A (en) * | 2021-04-09 | 2021-07-16 | 陕西科技大学 | Cellulose nano fibril suspension and preparation method thereof |
| CN116217991A (en) * | 2023-03-09 | 2023-06-06 | 四川大学 | Preparation method and application of circularly polarized light-emitting film |
| CN116751510A (en) * | 2023-07-10 | 2023-09-15 | 阿梓萨科技(深圳)有限公司 | Preparation method of photo-curing coating of acrylic resin composite nanocellulose |
| CN117461830A (en) * | 2023-11-14 | 2024-01-30 | 北京工商大学 | Cellulose nanofiber and sodium alginate composite microgel with lubricating effect and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103061174A (en) * | 2013-01-18 | 2013-04-24 | 中南林业科技大学 | Strong acid pretreatment assisted cellulose nano-filament preparation method |
| CN104293858A (en) * | 2013-07-19 | 2015-01-21 | 天津科技大学 | Preparation method for nano-microcrystalline cellulose |
| CN107653723A (en) * | 2017-09-11 | 2018-02-02 | 天津科技大学 | A kind of achievable chemi-mechanical pulp microfibril and the method for strengthening paper physical intensity |
-
2018
- 2018-01-25 CN CN201810074902.8A patent/CN108219008A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103061174A (en) * | 2013-01-18 | 2013-04-24 | 中南林业科技大学 | Strong acid pretreatment assisted cellulose nano-filament preparation method |
| CN104293858A (en) * | 2013-07-19 | 2015-01-21 | 天津科技大学 | Preparation method for nano-microcrystalline cellulose |
| CN107653723A (en) * | 2017-09-11 | 2018-02-02 | 天津科技大学 | A kind of achievable chemi-mechanical pulp microfibril and the method for strengthening paper physical intensity |
Non-Patent Citations (1)
| Title |
|---|
| GILBERTO SIQUEIRA等: ""Morphological investigation of nanoparticles obtained from combined mechanical shearing, and enzymatic and acid hydrolysis of sisal fibers"", 《CELLULOSE》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109096546A (en) * | 2018-07-27 | 2018-12-28 | 上海理工大学 | A method of high performance plastic film is produced using Cellulose nanocrystal body |
| CN109320616A (en) * | 2018-08-17 | 2019-02-12 | 东莞理工学院 | A kind of nano-cellulose and preparation method thereof of metal salt catalyst formic acid hydrolysis preparation |
| CN112725917A (en) * | 2020-12-28 | 2021-04-30 | 海南华创槟榔研究院 | Preparation method of areca seed cellulose nanofibrils |
| 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 |
| CN113123159A (en) * | 2021-04-09 | 2021-07-16 | 陕西科技大学 | Cellulose nano fibril suspension and preparation method thereof |
| CN113123159B (en) * | 2021-04-09 | 2022-11-22 | 陕西科技大学 | Cellulose nano-fibril suspension and preparation method thereof |
| CN116217991A (en) * | 2023-03-09 | 2023-06-06 | 四川大学 | Preparation method and application of circularly polarized light-emitting film |
| CN116217991B (en) * | 2023-03-09 | 2024-02-27 | 四川大学 | Preparation method and application of circularly polarized light-emitting film |
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