CN108300746A - A method of preparing nano micro crystal cellulose using wheatgrass cellulose microfibril as raw material - Google Patents
A method of preparing nano micro crystal cellulose using wheatgrass cellulose microfibril as raw material Download PDFInfo
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- CN108300746A CN108300746A CN201810090476.7A CN201810090476A CN108300746A CN 108300746 A CN108300746 A CN 108300746A CN 201810090476 A CN201810090476 A CN 201810090476A CN 108300746 A CN108300746 A CN 108300746A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
Abstract
The present invention relates to a kind of methods preparing nano micro crystal cellulose as raw material using wheatgrass cellulose microfibril, include the following steps：(1) wheat straw fiber is passed through to enzyme hydrolysis processing and high-pressure homogeneous processing successively, wheatgrass cellulose microfibril suspension is obtained, wheatgrass cellulose microfibril is dried to obtain by separation；(2) acid solution is added into wheatgrass cellulose microfibril, reacts 5~10h, deionized water is then added and stops reacting, stratification after sonic oscillation takes lower sediment to carry out washing dialysis, obtains nano micro crystal cellulose；Or wheatgrass cellulose microfibril and complex cellulase are added in sodium citrate buffer solution, water-bath 5~10h of oscillating reactions, obtain nano micro crystal cellulose using inactivation and washing.The present invention prepares nano micro crystal cellulose using wheatgrass cellulose microfibril as raw material, using cellulose abundant in discarded wheat straw waste, reduces the waste of resource, nano micro crystal cellulose yield obtained is high, and grain size is small, is evenly distributed.
Description
Technical field
The invention belongs to biomass nano Material Fields, and in particular to a kind of to be prepared by raw material of wheatgrass cellulose microfibril
The method of nano micro crystal cellulose.
Background technology
Cellulose is that source is most abundant in nature, is distributed most extensive, reproducible high-molecular organic material, is widely present
In cotton, timber, flax, in the plant cell walls such as careless class.The structure of cellulose macromolecule is divided into that several density are larger, molecule
The good crystal region of chain orientation and smaller, smaller to the intensity contribution amorphous region of density, a crystal region can be counted as micro-
Crystal.Cellulose microfibril be by native cellulose under great mechanism, or pretreatment combine mechanism remove
Out, diameter reaches the Cellulose functional materials of nanometer level.
Nano micro crystal cellulose is also referred to as nano cellulose crystal, is to be separated from native cellulose, and select
Selecting property retains the obtained biomass nano material in crystal region in cellulose.Nano micro crystal cellulose is relative to native cellulose
For there is special physics and chemical property, and the characteristics of remain native cellulose, have been obtained in recent years extensively
Research.
The wheat straw waste resource in China is very abundant, if annual a large amount of stalks directly burn, it will cause dirt to environment
Dye is unfavorable for sustainable development, and contains abundant cellulose in wheat straw waste, therefore will also result in the waste of resource.If
These cellulose resources can be processed to obtain Cellulose nanocrystal body, to higher value application, it will to environment, industry hair
Exhibition and efficiently using for resource play a positive role.
The method of production nano micro crystal cellulose mainly has Mechanical Method, chemical method and bioanalysis at present, also has pretreatment to tie
The method for closing machinery.Mechanical Method is to handle to obtain nano micro crystal cellulose to the physical mechanical of native cellulose progress high intensity,
Participation without chemicals, but processing procedure energy consumption is excessively high, while the nano micro crystal cellulose particle diameter distribution prepared is wide.Chemistry
Method directly acid, alkali process or oxidative degradation native cellulose can obtain nano micro crystal cellulose, but yield is relatively low and acts on
It is unevenly distributed, causes cellulosic degree of polymerization and the decline of fiber molecule quality and the waste of raw material, enzyme and chemicals.Biology
Nano micro crystal cellulose prepared by method is commonly known as bacteria cellulose, but that there are preparation process is complicated, yield is low, time-consuming and
The problems such as of high cost.
Invention content
It is an object of the invention to overcome problems of the prior art, provide one kind is with wheatgrass cellulose microfibril
The method that raw material prepares nano micro crystal cellulose, preparation process is simple, and the yield of nano micro crystal cellulose is high, and particle diameter distribution is equal
Even, function and effect are good, and can realize the higher value application of wheat straw waste.
In order to achieve the above object, the present invention adopts the following technical scheme that：
Include the following steps：
(1) wheat straw fiber is passed through to enzyme hydrolysis processing and high-pressure homogeneous processing successively, it is outstanding to obtain wheatgrass cellulose microfibril
Supernatant liquid is dried to obtain wheatgrass cellulose microfibril by separation；
(2) acid solution is added into wheatgrass cellulose microfibril, reacts 5~10h, deionized water is then added and stops instead
It answers, stratification after sonic oscillation takes lower sediment to carry out washing dialysis, obtains nano micro crystal cellulose；
Or wheatgrass cellulose microfibril and complex cellulase are added in sodium citrate buffer solution, water-bath oscillation is anti-
5~10h is answered, nano micro crystal cellulose is obtained using inactivation and washing.
Further, in step (1) enzyme hydrolysis handle comprise the concrete steps that：Wheat straw fiber is first configured to suspending liquid A, so
The complex cellulase of 5~10FPU/g over dry wheat straw fibers is added in backward suspending liquid A, in 45~50 DEG C of constant temperature oscillation water-baths
30~120min is reacted, after reaction through inactivation, washing, filtering and drying, completes enzyme hydrolysis processing.
Further, the mass fraction of suspending liquid A is 1%~3%.
Further, suspending liquid A is that sodium citrate buffer solution is added into over dry wheat straw fiber, immersion swollen 4~for 24 hours
It arrives；Hunting speed is 50~140r/min.
Further, step (1) mesohigh homogenization comprises the concrete steps that：The wheat straw fiber that enzyme hydrolysis is handled is made into
Suspension B, homogeneous 25~40 times, homogenization pressure complete high-pressure homogeneous processing in 60~120MPa.
Further, the mass fraction of suspension B is 0.2%~1.5%.
Further, in step (2) acid solution be mass concentration 40~50% sulfuric acid solution, wheatgrass cellulose microfibril
Ratio with sulfuric acid solution is 1g：(10~15) ml.
Further, 30~150min of ultrasound in step (2).
Further, the pH value of sodium citrate buffer solution is 4~5 in step (2), wheatgrass cellulose microfibril and citric acid
The ratio of sodium buffer solution is 1g：(10~13) ml.
Further, in step (2), the ratio of wheatgrass cellulose microfibril and complex cellulase is 1g：(2~5) ml.
Compared with prior art, the present invention has technique effect beneficial below：
The present invention one is to prepare nano micro crystal cellulose using wheatgrass cellulose microfibril as raw material, utilizes discarded wheat straw waste
In abundant cellulose prepare nano micro crystal cellulose, it is possible to reduce the higher value application of wheat straw waste is realized in the waste of resource.
It is by wheat straw fiber raw material through enzyme hydrolysis second is that using the nano micro crystal cellulose that wheatgrass cellulose microfibril is prepared as raw material, it is high
The wheatgrass cellulose microfibril that pressure homogenization obtains carries out sour water solution or enzyme hydrolysis obtains nano micro crystal cellulose, more traditional
The nano micro crystal cellulose yield that direct hydrolysis fibrous raw material obtains is high, and yield reaches 45.6~53.3%, and chemical cost is few,
Treatment effect is more preferable, obtain nano micro crystal cellulose grain size is small, distribution also evenly, average grain diameter is in 40~120nm.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for the nano micro crystal cellulose that acid hydrolyzed cellulose microfibril is prepared.
Fig. 2 is the scanning electron microscope (SEM) photograph for the nano micro crystal cellulose that sour water solution bleached wheat straw fiber obtains.
Fig. 3 is the scanning electron microscope (SEM) photograph for the nano micro crystal cellulose that enzyme hydrolysis cellulose microfibril is prepared.
Specific implementation mode
The present invention is described in further details below in conjunction with the accompanying drawings.
The present invention includes the following steps：
(1) solution
The sodium citrate buffer solution preparation method of pH value 4.0~5.0：Weigh 9.6 grams of anhydrous citric acids and 2.7 grams of hydroxides
Sodium is added in the distilled water of 900ml while agitating, and finally plus distilled water is settled to 1L.PH is tested, with citric acid or hydrogen
Sodium oxide molybdena dilute solution is adjusted to pH=4~5).
Complex cellulase (trade name Celluclast 1.5L are purchased from sigma companies, 50 DEG C of optimum temperature).
(2) enzyme pretreatment wheat straw fiber raw material
The over dry bleached wheat straw fiber for weighing certain mass is placed in conical flask, with the above-mentioned sodium citrate buffer solution prepared
It is configured to the suspension that mass fraction is 1.0%~3.0%, after fully impregnating swollen (4~for 24 hours), a certain amount of compound fibre is added
The plain enzyme (5~10FPU/g over dry wheat straw fiber) of dimension is then placed into 30~120min of hydrolysis in constant temperature oscillation water-bath, keeps water
45~50 DEG C of bath temperature, hunting speed are 50~140r/min.After reaction time to be achieved, inactivation 5min is boiled at once, is used
The repeated multiple times washing of distilled water, then use Buchner funnel vacuum filter, collect enzyme hydrolysis after fiber, after freeze-drying in case
After use.
(3) preparation of wheatgrass cellulose microfibril
The wheat straw fiber that a small amount of enzyme pretreatment is crossed is weighed, a concentration of 0.2%~1.5% fibrous suspension is configured to, into
Row is appropriate to be dispersed with stirring.Then, suspension is passed through into high-pressure homogeneous processing, repeatedly homogeneous 25~40 times, control pressure about 60
~120MPa prepares cellulose microfibril suspension.Suspension is centrifuged into 15~30min, rotating speed is 2500~5000r/
Min removes a layer pellet frozen drying, with spare.
(4) nano micro crystal cellulose is prepared
(401) sour water solution wheatgrass cellulose microfibril prepares nano micro crystal cellulose
Weigh certain mass over dry wheatgrass cellulose microfibril, be put into water bath chader, be slowly dropped into it is appropriate (10~
15ml) the sulfuric acid solution of mass concentration 40~50%.After reacting 5~10h, deionized water (about 200ml) is added and stops reaction.
With stratification after 30~150min of sonic oscillation instrument ultrasound, supernatant liquor is removed, to lower sediment centrifuge washing, centrifugal basket
Speed is 3500~5000r/min, and washing is until suspension no longer settles repeatedly.Suspension is moved into bag filter, then
Dialysis in deionized water is put into until pH is close to 7, the suspension after having dialysed is put into refrigerator (3.0~5.0 DEG C) preservations.
(402) enzyme hydrolysis wheatgrass cellulose microfibril prepares nano micro crystal cellulose
Certain mass over dry wheatgrass cellulose microfibril is weighed, the above-mentioned sodium citrate buffer solutions prepared of 10~13ml are added
(may be used and the identical sodium citrate buffer solution of step (2)) is put into water bath chader.Compound fibre is slowly added in right amount again
Dimension 2~5ml of plain enzyme, after reacting 5~10h, taking-up inactivates 5min in boiling water, carries out centrifuge washing, centrifuge speed 3500
~5000r/min, repeatedly washing until suspension no longer settle, collect nano micro crystal cellulose suspension.
The present invention prepares nano micro crystal cellulose using wheatgrass cellulose microfibril as raw material, and it is micro- to expand wheatgrass cellulose
The application range of fibril realizes that high-qualityization of wheat straw waste utilizes, new thinking is provided for the preparation of nano micro crystal cellulose.
The nano micro crystal cellulose prepared using the wheatgrass cellulose microfibril sour hydrolysis fiber raw material more traditional as raw material
Yield is high, and treatment effect is more preferable, obtain nano micro crystal cellulose grain size is small, distribution also evenly.
With reference to the preparation condition of nano micro crystal cellulose in the present invention and the degree of polymerization, the grain of nano micro crystal cellulose
The invention will be further described for diameter distribution etc., and following non-limiting examples can make those skilled in the art more
It is apparent from the present invention, but do not limit the invention in any way.
Embodiment 1
It weighs 3g over dry bleached wheat straw fibers to be placed in the conical flask of 250mL, be matched with the sodium citrate buffer solution of Ph=5.0
The pulp suspension that mass fraction is 3.0% is made, after impregnating swollen 4h, adds according to relative to over dry wheat straw fiber 10FPU/g
Enter complex cellulase, then conical flask is placed into constant temperature oscillation water-bath and hydrolyzes 30min, keeps water bath chader temperature
45 DEG C, hunting speed 80r/min.After reaction time to be achieved, inactivation 5min is boiled at once, is washed with distilled water is repeated multiple times
It washes, then uses Buchner funnel vacuum filter, collect the fiber after enzyme hydrolysis, after freeze-drying for future use.
The suspension that the wheat straw fiber that 3g enzyme pretreatments are crossed is configured to a concentration of 0.2% is weighed, stirring point appropriate is carried out
It dissipates.Then, suspension is passed through into high-pressure homogeneous processing, repeatedly homogeneous 40 times, control pressure about 60MPa prepares wheat straw fiber
Plain microfibril.Suspension is centrifuged into 15min, rotating speed 5000r/min, a layer pellet frozen drying is removed, with spare.
1g over dry wheatgrass cellulose microfibrils are weighed in 250ml conical flasks, is put into water bath chader, is slowly dropped into
50% sulfuric acid solution 10ml after reacting 5h, is added deionized water (about 200ml) and stops reaction.With sonic oscillation instrument ultrasound
1h is stood after 150min, removes supernatant liquor, to lower sediment centrifuge washing, centrifuge speed 3500r/min is washed repeatedly
It is no longer settled under this rotating speed to suspension.Suspension is moved into bag filter, is then placed in deionized water and dialyses directly
To pH close to 7, the suspension after having dialysed is put into refrigerator (3.0 DEG C) preservations.The nano micro crystal cellulose obtained after dialysis
Soliquid blueing light.
Obtained nano micro crystal cellulose is as shown in Figure 1, be in club shaped structure, and particle size distribution range is small.By detection, receive
Rice microcrystalline cellulose yield is 49%, average degree of polymerization 143, cationic demand 42.6, grain size is mainly distributed on 50~
Between 110nm (size being bar-like on the length direction of nano micro crystal cellulose more than 100nm), comparison wheatgrass cellulose and
The infrared spectrum of wheatgrass cellulose microfibril, not new functional group generate, and the crystal form that X-ray diffraction also measures product is not sent out
Changing, crystallinity 70.33%, molecular mass 23166.
Comparative example 1：
1g over dry bleached wheat straw fibers are weighed in 250mL conical flasks, 50% sulfuric acid solution 10ml is slowly dropped into, is put into water
It bathes in oscillator, keeps water bath chader temperature 50 C, hunting speed 80r/min.After reacting 5.5h, deionized water is added
(about 200mL) stops reaction.After standing 1h after sonic oscillation instrument ultrasound 150min, supernatant liquor is removed, to lower sediment
Centrifuge washing, centrifuge speed 3500r/min, washing is until suspension no longer settles under this rotating speed repeatedly.It will hang
Supernatant liquid moves into bag filter, is then placed in dialysis in deionized water until pH is close to 7, the suspension after having dialysed is put into refrigerator
In (3.0 DEG C) preservation.The Nanocrystalline Cellulose Colloid suspension blueing light obtained after dialysis.
Obtained nano micro crystal cellulose is as shown in Figure 2, it can be seen that nano micro crystal cellulose is in club shaped structure, grain size more
It is larger to be distributed distribution.By detection, nano micro crystal cellulose yield is 28.4%, and average degree of polymerization 118, cation needs
The amount of asking is 48.3, and grain size is mainly distributed between 45-300nm, compares the infrared spectrum of wheatgrass cellulose, not new functional group
It generates, the crystal form that X-ray diffraction also measures product does not change, crystallinity 69.44%, molecular mass 19116.
Sour water solution wheatgrass cellulose microfibril and sour water solution wheat straw fiber it can be seen from above example 1 and comparative example 1
The variation of raw material obtained product Jun Weiyou functional groups, crystal form also do not change, but yield is higher by by about one time, and
Particle size distribution range smaller.It can be said that bright, the present invention is fine by the obtained nano microcrystalline of acid hydrolyzed cellulose microfibril
The plain yield higher of dimension, particle diameter distribution are more uniform.
Embodiment 2：
It weighs 3g over dry bleached wheat straw fibers to be placed in the conical flask of 250mL, be matched with the sodium citrate buffer solution of Ph=5.0
The pulp suspension that mass fraction is 3.0% is made, after impregnating swollen 4h, adds according to relative to over dry wheat straw fiber 10FPU/g
Enter complex cellulase, then conical flask is placed into constant temperature oscillation water-bath and hydrolyzes 30min, keeps water bath chader temperature
45 DEG C, hunting speed 80r/min.After reaction time to be achieved, inactivation 5min is boiled at once, is washed with distilled water is repeated multiple times
It washes, then uses Buchner funnel vacuum filter, collect the fiber after enzyme hydrolysis, after freeze-drying for future use.
The suspension that the wheat straw fiber that 3g enzyme pretreatments are crossed is configured to a concentration of 0.2% is weighed, stirring point appropriate is carried out
It dissipates.Then, suspension is passed through into high-pressure homogeneous processing, repeatedly homogeneous 40 times, control pressure about 60MPa prepares wheat straw fiber
Plain microfibril.Suspension is centrifuged into 15min, rotating speed 5000r/min, a layer pellet frozen drying is removed, with spare.
1g over dry wheatgrass cellulose microfibrils are weighed in 250ml conical flasks, 12ml sodium citrate buffer solutions are added and are put into
In water bath chader.0.05mol/l compound cellulose enzyme solutions 3ml are slow added into, after reacting 5h, taking-up inactivates in boiling water
5min carries out centrifuge washing, and centrifuge speed 3500r/min, washing is until suspension no longer occurs under this rotating speed repeatedly
Nano micro crystal cellulose suspension is collected in sedimentation.
Obtained nano micro crystal cellulose is as shown in figure 3, be in chondritic, size is smaller.By detection, nano microcrystalline is fine
The plain yield of dimension is 53.3%, average degree of polymerization 175, cationic demand 37.2, grain size be mainly distributed on 80~120nm it
Between, the infrared spectrum of wheatgrass cellulose and wheatgrass cellulose microfibril is compared, not new functional group generates, X-ray diffraction
The crystal form for measuring product does not change, crystallinity 74.23%, molecular mass 28350.
Embodiment 3：
It weighs 3g over dry bleached wheat straw fibers to be placed in the conical flask of 250mL, be matched with the sodium citrate buffer solution of Ph=4.8
The pulp suspension that mass fraction is 2.0% is made, after impregnating swollen 10h, adds according to relative to over dry wheat straw fiber 8FPU/g
Enter complex cellulase, then conical flask is placed into constant temperature oscillation water-bath and hydrolyzes 60min, keeps water bath chader temperature
46 DEG C, hunting speed 100r/min.After reaction time to be achieved, inactivation 5min is boiled at once, is washed with distilled water is repeated multiple times
It washes, then uses Buchner funnel vacuum filter, collect the fiber after enzyme hydrolysis, after freeze-drying for future use.
The suspension that the wheat straw fiber that 3g enzyme pretreatments are crossed is configured to a concentration of 0.6% is weighed, stirring point appropriate is carried out
It dissipates.Then, suspension is passed through into high-pressure homogeneous processing, repeatedly homogeneous 32 times, control pressure about 80MPa prepares wheat straw fiber
Plain microfibril.Suspension is centrifuged into 20min, rotating speed 4000r/min, a layer pellet frozen drying is removed, with spare.
1g over dry wheatgrass cellulose microfibrils are weighed in 250ml conical flasks, is put into water bath chader, is slowly dropped into
47% sulfuric acid solution 12ml after reacting 7h, is added deionized water (about 200ml) and stops reaction.With sonic oscillation instrument ultrasound
1h is stood after 100min, removes supernatant liquor, to lower sediment centrifuge washing, centrifuge speed 4000r/min is washed repeatedly
Until suspension no longer settles under this rotating speed.Suspension is moved into bag filter, is then placed in deionized water and dialyses
Until pH, close to 7, the suspension after having dialysed is put into refrigerator (3.0 DEG C) preservations.
Obtained nano micro crystal cellulose is in club shaped structure, and particle size distribution range is small.By detection, nano microcrystalline fiber
Plain yield is 45.6%, and average degree of polymerization 131, cationic demand 49.5, grain size is mainly distributed between 60~110nm
(size being bar-like on the length direction of nano micro crystal cellulose more than 100nm) compares wheatgrass cellulose and wheat straw fiber
The infrared spectrum of plain microfibril, not new functional group generate, and the crystal form that X-ray diffraction also measures product does not change, tie
Brilliant degree is 75.60%, molecular mass 24903.
Embodiment 4：
It weighs 3g over dry bleached wheat straw fibers to be placed in the conical flask of 250mL, be matched with the sodium citrate buffer solution of Ph=4.8
The pulp suspension that mass fraction is 2.0% is made, after impregnating swollen 10h, adds according to relative to over dry wheat straw fiber 8FPU/g
Enter complex cellulase, then conical flask is placed into constant temperature oscillation water-bath and hydrolyzes 60min, keeps water bath chader temperature
46 DEG C, hunting speed 100r/min.After reaction time to be achieved, inactivation 5min is boiled at once, is washed with distilled water is repeated multiple times
It washes, then uses Buchner funnel vacuum filter, collect the fiber after enzyme hydrolysis, after freeze-drying for future use.
The suspension that the wheat straw fiber that 3g enzyme pretreatments are crossed is configured to a concentration of 0.6% is weighed, stirring point appropriate is carried out
It dissipates.Then, suspension is passed through into high-pressure homogeneous processing, repeatedly homogeneous 32 times, control pressure about 80MPa prepares wheat straw fiber
Plain microfibril.Suspension is centrifuged into 20min, rotating speed 4000r/min, a layer pellet frozen drying is removed, with spare.
1g over dry wheatgrass cellulose microfibrils are weighed in 250ml conical flasks, 10ml sodium citrate buffer solutions are added and are put into
In water bath chader.0.05mol/l compound cellulose enzyme solutions 5ml are slow added into, after reacting 5h, taking-up inactivates in boiling water
5min carries out centrifuge washing, and centrifuge speed 4000r/min, washing is until suspension no longer occurs under this rotating speed repeatedly
Nano micro crystal cellulose suspension is collected in sedimentation.
Obtained nano micro crystal cellulose is in chondritic, and size is smaller.By detection, nano micro crystal cellulose yield is
49.9%, average degree of polymerization 142, cationic demand 41.8, grain size is mainly distributed between 40~100nm, compares wheat
The infrared spectrum of grass fiber element and wheatgrass cellulose microfibril, not new functional group generate, and X-ray diffraction also measures product
Crystal form do not change, crystallinity 79.48%, molecular mass 33142.
Embodiment 5：
It weighs 3g over dry bleached wheat straw fibers to be placed in the conical flask of 250mL, be matched with the sodium citrate buffer solution of Ph=4.5
The pulp suspension that mass fraction is 1.5% is made, after impregnating swollen 18h, adds according to relative to over dry wheat straw fiber 6FPU/g
Enter complex cellulase, then conical flask is placed into constant temperature oscillation water-bath and hydrolyzes 90min, keeps water bath chader temperature
48 DEG C, hunting speed 140r/min.After reaction time to be achieved, inactivation 5min is boiled at once, is washed with distilled water is repeated multiple times
It washes, then uses Buchner funnel vacuum filter, collect the fiber after enzyme hydrolysis, after freeze-drying for future use.
The suspension that the wheat straw fiber that 3g enzyme pretreatments are crossed is configured to a concentration of 1.0% is weighed, stirring point appropriate is carried out
It dissipates.Then, suspension is passed through into high-pressure homogeneous processing, repeatedly homogeneous 28 times, control pressure about 100MPa prepares wheat straw fiber
Plain microfibril.Suspension is centrifuged into 25min, rotating speed 3200r/min, a layer pellet frozen drying is removed, with spare.
1g over dry wheatgrass cellulose microfibrils are weighed in 250ml conical flasks, is put into water bath chader, is slowly dropped into
45% sulfuric acid solution 13ml after reacting 8h, is added deionized water (about 200ml) and stops reaction.With sonic oscillation instrument ultrasound
1h is stood after 60min, removes supernatant liquor, to lower sediment centrifuge washing, centrifuge speed 4500r/min is washed repeatedly
Until suspension no longer settles under this rotating speed.Suspension is moved into bag filter, is then placed in deionized water and dialyses
Until pH, close to 7, the suspension after having dialysed is put into refrigerator (3.0 DEG C) preservations.
Embodiment 6：
It weighs 3g over dry bleached wheat straw fibers to be placed in the conical flask of 250mL, be matched with the sodium citrate buffer solution of Ph=4.5
The pulp suspension that mass fraction is 1.5% is made, after impregnating swollen 18h, adds according to relative to over dry wheat straw fiber 6FPU/g
Enter complex cellulase, then conical flask is placed into constant temperature oscillation water-bath and hydrolyzes 90min, keeps water bath chader temperature
48 DEG C, hunting speed 140r/min.After reaction time to be achieved, inactivation 5min is boiled at once, is washed with distilled water is repeated multiple times
It washes, then uses Buchner funnel vacuum filter, collect the fiber after enzyme hydrolysis, after freeze-drying for future use.
The suspension that the wheat straw fiber that 3g enzyme pretreatments are crossed is configured to a concentration of 1.0% is weighed, stirring point appropriate is carried out
It dissipates.Then, suspension is passed through into high-pressure homogeneous processing, repeatedly homogeneous 28 times, control pressure about 100MPa prepares wheat straw fiber
Plain microfibril.Suspension is centrifuged into 25min, rotating speed 3200r/min, a layer pellet frozen drying is removed, with spare.
1g over dry wheatgrass cellulose microfibrils are weighed in 250ml conical flasks, 11ml sodium citrate buffer solutions are added and are put into
In water bath chader.0.05mol/l compound cellulose enzyme solutions 4ml are slow added into, after reacting 7h, taking-up inactivates in boiling water
5min carries out centrifuge washing, and centrifuge speed 4500r/min, washing is until suspension no longer occurs under this rotating speed repeatedly
Nano micro crystal cellulose suspension is collected in sedimentation.
Embodiment 7：
It weighs 3g over dry bleached wheat straw fibers to be placed in the conical flask of 250mL, be matched with the sodium citrate buffer solution of Ph=4.0
The pulp suspension that mass fraction is 1.0% is made, after impregnating swollen for 24 hours, adds according to relative to over dry wheat straw fiber 5FPU/g
Enter complex cellulase, then conical flask is placed into constant temperature oscillation water-bath and hydrolyzes 120min, keeps water bath chader temperature
50 DEG C of degree, hunting speed 50r/min.After reaction time to be achieved, inactivation 5min is boiled at once, is washed with distilled water is repeated multiple times
It washes, then uses Buchner funnel vacuum filter, collect the fiber after enzyme hydrolysis, after freeze-drying for future use.
The suspension that the wheat straw fiber that 3g enzyme pretreatments are crossed is configured to a concentration of 1.5% is weighed, stirring point appropriate is carried out
It dissipates.Then, suspension is passed through into high-pressure homogeneous processing, repeatedly homogeneous 25 times, control pressure about 120MPa prepares wheat straw fiber
Plain microfibril.Suspension is centrifuged into 30min, rotating speed 2500r/min, a layer pellet frozen drying is removed, with spare.
1g over dry wheatgrass cellulose microfibrils are weighed in 250ml conical flasks, is put into water bath chader, is slowly dropped into
40% sulfuric acid solution 15ml after reacting 10h, is added deionized water (about 200ml) and stops reaction.With sonic oscillation instrument ultrasound
1h is stood after 30min, removes supernatant liquor, to lower sediment centrifuge washing, centrifuge speed 5000r/min is washed repeatedly
Until suspension no longer settles under this rotating speed.Suspension is moved into bag filter, is then placed in deionized water and dialyses
Until pH, close to 7, the suspension after having dialysed is put into refrigerator (3.0 DEG C) preservations.
Embodiment 8：
It weighs 3g over dry bleached wheat straw fibers to be placed in the conical flask of 250mL, be matched with the sodium citrate buffer solution of Ph=4.0
The pulp suspension that mass fraction is 1.0% is made, after impregnating swollen for 24 hours, adds according to relative to over dry wheat straw fiber 5FPU/g
Enter complex cellulase, then conical flask is placed into constant temperature oscillation water-bath and hydrolyzes 120min, keeps water bath chader temperature
50 DEG C of degree, hunting speed 50r/min.After reaction time to be achieved, inactivation 5min is boiled at once, is washed with distilled water is repeated multiple times
It washes, then uses Buchner funnel vacuum filter, collect the fiber after enzyme hydrolysis, after freeze-drying for future use.
The suspension that the wheat straw fiber that 3g enzyme pretreatments are crossed is configured to a concentration of 1.5% is weighed, stirring point appropriate is carried out
It dissipates.Then, suspension is passed through into high-pressure homogeneous processing, repeatedly homogeneous 25 times, control pressure about 120MPa prepares wheat straw fiber
Plain microfibril.Suspension is centrifuged into 30min, rotating speed 2500r/min, a layer pellet frozen drying is removed, with spare.
1g over dry wheatgrass cellulose microfibrils are weighed in 250ml conical flasks, 13ml sodium citrate buffer solutions are added and are put into
In water bath chader.0.05mol/l compound cellulose enzyme solutions 2ml are slow added into, after reacting 10h, taking-up is gone out in boiling water
5min living carries out centrifuge washing, and centrifuge speed 3500r/min, washing is until suspension is no longer sent out under this rotating speed repeatedly
Raw sedimentation, collects nano micro crystal cellulose suspension.
The present invention provides a kind of methods preparing nano micro crystal cellulose by wheatgrass cellulose microfibril, first by wheat straw fibre
Dimension raw material obtains cellulose microfibril with the add high pressure method of homogeneous of enzyme pretreatment, then carries out acid or enzyme hydrolysis processing, is nanometer
The preparation of microcrystalline cellulose provides new thinking, and is conducive to expand the height of the application and wheat straw waste of cellulose microfibril
Value utilizes.
Claims (10)
1. a kind of method preparing nano micro crystal cellulose as raw material using wheatgrass cellulose microfibril, it is characterised in that：Including with
Lower step：
(1) wheat straw fiber is passed through to enzyme hydrolysis processing and high-pressure homogeneous processing successively, obtains wheatgrass cellulose microfibril suspension,
It is dried to obtain wheatgrass cellulose microfibril by separation；
(2) acid solution is added into wheatgrass cellulose microfibril, reacts 5~10h, deionized water is then added and stops reaction, surpasses
Stratification after sound oscillation takes lower sediment to carry out washing dialysis, obtains nano micro crystal cellulose；
Or wheatgrass cellulose microfibril and complex cellulase are added in sodium citrate buffer solution, water-bath oscillating reactions 5
~10h obtains nano micro crystal cellulose using inactivation and washing.
2. a kind of side preparing nano micro crystal cellulose using wheatgrass cellulose microfibril as raw material according to claim 1
Method, it is characterised in that：What enzyme hydrolysis was handled in step (1) comprises the concrete steps that：Wheat straw fiber is first configured to suspending liquid A, then
The complex cellulase of 5~10FPU/g over dry wheat straw fibers is added into suspending liquid A, it is anti-in 45~50 DEG C of constant temperature oscillation water-baths
30~120min is answered, after reaction through inactivation, washing, filtering and drying, completes enzyme hydrolysis processing.
3. a kind of side preparing nano micro crystal cellulose using wheatgrass cellulose microfibril as raw material according to claim 2
Method, it is characterised in that：The mass fraction of suspending liquid A is 1%~3%.
4. a kind of side preparing nano micro crystal cellulose using wheatgrass cellulose microfibril as raw material according to claim 2
Method, it is characterised in that：Suspending liquid A is that sodium citrate buffer solution is added into over dry wheat straw fiber, immersion swollen 4~obtain for 24 hours
's；Hunting speed is 50~140r/min.
5. a kind of side preparing nano micro crystal cellulose using wheatgrass cellulose microfibril as raw material according to claim 1
Method, it is characterised in that：Step (1) mesohigh homogenization comprises the concrete steps that：The wheat straw fiber that enzyme hydrolysis is handled is made into outstanding
Supernatant liquid B, homogeneous 25~40 times, homogenization pressure complete high-pressure homogeneous processing in 60~120MPa.
6. a kind of side preparing nano micro crystal cellulose using wheatgrass cellulose microfibril as raw material according to claim 5
Method, it is characterised in that：The mass fraction of suspension B is 0.2%~1.5%.
7. a kind of side preparing nano micro crystal cellulose using wheatgrass cellulose microfibril as raw material according to claim 1
Method, it is characterised in that：Acid solution is the sulfuric acid solution of mass concentration 40~50% in step (2), wheatgrass cellulose microfibril and
The ratio of sulfuric acid solution is 1g：(10~15) ml.
8. a kind of side preparing nano micro crystal cellulose using wheatgrass cellulose microfibril as raw material according to claim 1
Method, it is characterised in that：30~150min of ultrasound in step (2).
9. a kind of side preparing nano micro crystal cellulose using wheatgrass cellulose microfibril as raw material according to claim 1
Method, it is characterised in that：The pH value of sodium citrate buffer solution is 4~5 in step (2), wheatgrass cellulose microfibril and sodium citrate
The ratio of buffer solution is 1g：(10~13) ml.
10. a kind of side preparing nano micro crystal cellulose using wheatgrass cellulose microfibril as raw material according to claim 1
Method, it is characterised in that：In step (2), the ratio of wheatgrass cellulose microfibril and complex cellulase is 1g：(2~5) ml.
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| CN113087809A (en) * | 2021-04-16 | 2021-07-09 | 河南工业大学 | Preparation of novel nano-cellulose with high strength and high crystallinity |
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| CN113087809A (en) * | 2021-04-16 | 2021-07-09 | 河南工业大学 | Preparation of novel nano-cellulose with high strength and high crystallinity |
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