CN104910394B - A kind of method that graphene oxide co-catalysis sour water solution prepares nano micro crystal cellulose - Google Patents
A kind of method that graphene oxide co-catalysis sour water solution prepares nano micro crystal cellulose Download PDFInfo
- Publication number
- CN104910394B CN104910394B CN201510273595.2A CN201510273595A CN104910394B CN 104910394 B CN104910394 B CN 104910394B CN 201510273595 A CN201510273595 A CN 201510273595A CN 104910394 B CN104910394 B CN 104910394B
- Authority
- CN
- China
- Prior art keywords
- micro crystal
- nano micro
- cellulose
- graphene oxide
- crystal cellulose
- 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.)
- Active
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of method that graphene oxide co-catalysis sour water solution prepares nano micro crystal cellulose, its method is to prepare certain density sulfuric acid oxidation Graphene mixed solution, and it is slowly added to microcrystalline cellulose powder while stirring, question response adds distilled water terminating reaction after terminating, carry out centrifugation extraction, the Nanocrystalline Cellulose Colloid dialysis that will be collected is until neutrality, eventually passes freeze-drying and obtain nano micro crystal cellulose powder.Main innovation point of the invention is to obtain nano micro crystal cellulose using graphene oxide co-catalysis acid hydrolyzing microcrystalline cellulose；Using graphene oxide hierarchy and the abundant adjacent carboxyl of carbonyl promotion and phenolic hydroxyl group hydrolysis flexibly, soft, to improve the yield of nano micro crystal cellulose, with most important theories meaning and more practical value.
Description
Technical field
The present invention relates to a kind of preparation method of nano micro crystal cellulose.This invention is with microcrystalline cellulose as former
Material, sulfuric acid are reaction acid, are catalyst auxiliary catalysis sour water solution improving the yield of nano micro crystal cellulose with graphene oxide.
Background technology
Cellulose is to be widely present on the earth and reproducible resource.Nano micro crystal cellulose, is that native cellulose passes through
Treatment（Such as sour water solution, biological enzyme hydrolysis）Afterwards, in cellulose amorphous region and the crystal region of low-crystallinity is abolished, and is obtained
A kind of cellulose crystallite body for arriving.The nano micro crystal cellulose prepared by native cellulose not only has the basic structure of cellulose
With performance, also with huge specific surface area（~70）, high-crystallinity（>70%）, high-hydrophilic, high Young's modulus, high intensity
(7500MPa), hyperfine structure and high transparency, good biodegradability is with biocompatibility and stabilization chemically
Energy.In addition, because cellulose surface exposes great amount of hydroxy group, reproducibility and non-reducing end group so that nano micro crystal cellulose
With huge chemical modification potentiality, promoting its application study in fields such as papermaking, medicine, food, composites to process hand can
Heat.Huge application potential is especially shown in terms of enhancing by polymer.For example, Dubief etc.（Macromolecules,
1999, 32(18): 5765-5771）Have studied in detail rod-like nano- crystalline cellulose and poly- 3- hydroxyls monooctyl ester latex it is compound after
The enhancing effect of the nano composite membrane for preparing, and contrasted with the enhancing effect of starch fibril, with starch fibril phase
Than nano micro crystal cellulose can just reach fabulous enhancing effect in very low levels.Grunert etc.（Journal of
Polymers and the Environment, 2002, 10(1-2): 27-30）To nano micro crystal cellulose and through trimethyl
The influence of the NCC enhancing acetylbutyrylcelluloses after Si modification is studied, and as a result shows no matter add modified and unmodified
Nano micro crystal cellulose, the storage modulus of acetylbutyrylcellulose can be greatly improved.Ji Jianfeng etc.（Chinese papermaking
Report, 2014,29 (2): 18-22）With nano micro crystal cellulose as skeleton, Hexafluorobutyl mathacrylate is monomer, by breast
Liquid glycerol polymerization synthesizing new Cypres, and carry out the application study of top sizing.Investigate emulsifier and fluorine-containing list
Body and influence of the nano micro crystal cellulose mass ratio to grafting rate, grafting efficiency and monomer conversion；It is modified under the conditions of more excellent
Nano micro crystal cellulose grafting rate, grafting efficiency, monomer conversion are respectively 125.2%, 27.7%, 90.1%.Result of study table
Bright, gained modified Nano microcrystalline cellulose has good stability in emulsion system；Top sizing is used it for, at applying glue
Paper contact angle after reason can reach 120 °, and tensile index can improve 26.4% compared with the paper using unmodified NCC, reach
22.0 N·m/g。
At present, the topmost preparation method of nano micro crystal cellulose is acid-hydrolysis method, the nano microcrystalline that acid-hydrolysis method is obtained
Cellulose maintains the crystal formation of cellulose script, and wherein sulfuric acid is topmost acid, nano microcrystalline fiber prepared by sulphuric acid hydrolysis
Procatarxis is negatively charged for substantial amounts of sulfonic acid group is introduced on surface, can be stably dispersed in water.However, simple sour water
The yield that solution prepares nano micro crystal cellulose is not very high.It is well known that production yield determines nano micro crystal cellulose
Economy and producing feasibility.Therefore, research and development preparing craft improves the production yield of nano micro crystal cellulose
With most important theories meaning and more practical value.
The content of the invention
For this problem, nano microcrystalline is prepared it is an object of the invention to provide a kind of graphene oxide co-catalysis sour water solution fine
The method for tieing up element.Sulphuric acid hydrolysis ensure that the intrinsic crystal formation of nano micro crystal cellulose and can in water stable dispersion, graphite oxide
The addition of alkene promotes the efficiency of hydrolysis, improves the yield of nano micro crystal cellulose, and whole experiment process is easy to operate
It is controllable.
The purpose of the present invention is achieved through the following technical solutions：
（1）First, take a certain amount of graphite oxide to be placed in beaker, add a certain amount of distilled water, be in ultrasonic power
Taken out after ultrasound is peeled off 2 hours in the ultrasonic cleaning instrument of 100W.The concentrated sulfuric acid that a certain amount of mass fraction is 98% is added, is prepared
Into the sulfuric acid oxidation Graphene mixed solution that mass fraction is 65%, sulfuric acid oxidation Graphene mixed solution to be diluted is cooled to
After room temperature, it is moved into there-necked flask, a certain amount of microcrystalline cellulose powder is slowly added under 400r/min mixing speeds, mixes
Start timing after closing uniformly, after persistently carrying out acid hydrolytic reaction certain hour under certain bath temperature, add 400mL distilled water
Terminating reaction.
（2）Secondly, by step（1）In the nano micro crystal cellulose that is obtained by graphene oxide auxiliary catalysis sulphuric acid hydrolysis mix
Close liquid and 10min be centrifuged under 11000r/min rotating speeds, outwell supernatant, repeat above-mentioned centrifugally operated up to upper liquid becomes cloudy,
Start to collect nano micro crystal cellulose, repeated centrifugation operation becomes clear again up to upper liquid, stops collecting.By receiving that collection is obtained
Rice microcrystal cellulose colloid is placed in the bag filter that specification is 8000~14000 is dialysed 2~3 days, and a dialyzate is changed every 2h,
Dialyzate is distilled water, finally obtains pH close to neutral Nanocrystalline Cellulose Colloid.
（3）Finally, by step（2）In neutral Nanocrystalline Cellulose Colloid freeze-drying in freeze drier for obtaining
48h, that is, obtain nano micro crystal cellulose powder.
Step of the present invention（1）Middle graphite oxide is obtained through the oxidation of following technique by graphite：1. 5g powdered graphites, 2.5g are taken
Sodium nitrate and 60 milliliter of 98% sulfuric acid are placed in there-necked flask, are stirred at room temperature 30 minutes, and rotating speed is 400rpm；2. it is then placed in water
In bath, keep reaction temperature below 20 DEG C, be slowly added to 15g potassium permanganate, control the addition time for 0.5 hour, add
Stir 2 hours afterwards, whole reaction temperature is all controlled below 20 DEG C；3. 50 milliliters of distilled water then are added dropwise over, then are warmed up to
35 DEG C, stir 2 hours；4. 100 milliliters of water are disposably added after, 95 DEG C are warmed up to, continues to react 15 minutes；5. 10mL is added
Mass fraction is 30% hydrogen peroxide, and stirring is taken out after 10 minutes, plus 1000 milliliters of distilled water dilutings；6. obtained mixed liquor is entered
Row vacuum filtration, then drying obtains graphite oxide.Step（1）Middle microcrystalline cellulose powder quality and mass fraction are 65%
Sulfuric acid solution volume ratio is 1:10, i.e. solid-to-liquid ratio are 1:10；Step（2）In every time centrifuge washing add amount of distilled water for 25ml~
35ml；Step（1）Described in graphene oxide add quality for microcrystalline cellulose 2%~6%.
Beneficial effects of the present invention：
First, it is catalyzed with graphene oxide during acidolysis, graphene oxide has multilayer morphosis in itself
It is soft and flexible, while abundant carbonyl has facilitation for the hydrolysis of carboxyl and phenolic hydroxyl group, therefore with graphite oxide
When alkene makees catalyst, the sour water solution that the yield of nano micro crystal cellulose is more simple is significantly improved.
2nd, sulphuric acid hydrolysis ensure that the original cellulose crystal formation of the nano micro crystal cellulose of preparation, the introducing of sulfonic acid group
When nano micro crystal cellulose be stably dispersed in water, can preserve for a long time；Preparation technology flow is simple, and easy to operate and control,
To cellulose degradation not damaged.
Specific embodiment
The inventive method is described further with reference to embodiments.
Embodiment 1：
（1）First, the graphite oxide for taking 0.1g is placed in beaker, adds a certain amount of distilled water, is in ultrasonic power
Ultrasound is taken out after peeling off 2h in the ultrasonic cleaning instrument of 100W.The concentrated sulfuric acid for adding a certain amount of mass fraction to be 98%, is configured to matter
Amount fraction is 65% sulfuric acid oxidation Graphene mixed solution, after sulfuric acid solution to be diluted is cooled to room temperature, is moved into three mouthfuls of burnings
In bottle, the microcrystalline cellulose powder of 5g is slowly added under 400r/min mixing speeds, starts timing after being well mixed, at 50 DEG C
Under bath temperature after sustained response 1.5h, 400mL distilled water terminating reactions are added.
（2）Secondly, by step（1）In the nano micro crystal cellulose that is obtained by graphene oxide auxiliary catalysis sulphuric acid hydrolysis mix
Close liquid and 10min be centrifuged under 11000r/min rotating speeds, outwell supernatant, repeat above-mentioned centrifugally operated up to upper liquid becomes cloudy,
Start to collect nano micro crystal cellulose, repeated centrifugation operation becomes clear again up to upper liquid, stops collecting.By receiving that collection is obtained
Rice microcrystal cellulose colloid is placed in the bag filter that specification is 8000~14000 is dialysed 2~3 days, and a dialyzate is changed every 2h,
Dialyzate is distilled water, finally obtains pH close to neutral Nanocrystalline Cellulose Colloid.
（3）Finally, by step（2）In neutral Nanocrystalline Cellulose Colloid freeze-drying in freeze drier for obtaining
48h, that is, obtain nano micro crystal cellulose powder.
This implementation steps（1）Middle graphite oxide is obtained through the oxidation stripping of following technique by graphite：1. 5g graphite oxides,
2.5g sodium nitrate and 60 milliliter of 98% sulfuric acid are placed in there-necked flask, and 30min is stirred at room temperature, and rotating speed is 400rpm；2. it is then placed in water
Bath, is kept for less than 20 DEG C, is slowly added to 15g potassium permanganate, controls the addition time for 0.5 hour, and 2h is stirred after adding, whole
Temperature is all controlled below 20 DEG C；3. 50mL distilled water is then added dropwise over, then is warmed up to 35 DEG C, stirring 2h；4. added after
100mL water, is warmed up to 95 DEG C, reacts 15min；5. it is 30% hydrogen peroxide to add 10mL mass fractions, reacts 10min, is taken out, plus
1000mL water dilutes；6. obtained mixed liquor is carried out into vacuum filtration, then drying obtains graphite oxide.Step（1）Middle crystallite
Cellulose powder quality is 1 with sulfuric acid volume ratio: 10；Step（2）In every time centrifuge washing add amount of distilled water for 25ml~
35ml.The yield of nano micro crystal cellulose prepared by this experiment is about 41.80%.
Embodiment 2：
（1）First, the graphite oxide for taking 0.2g is placed in beaker, adds a certain amount of distilled water, is in ultrasonic power
Ultrasound is taken out after peeling off 2h in the ultrasonic cleaning instrument of 100W.The concentrated sulfuric acid for adding a certain amount of mass fraction to be 98%, is configured to matter
Amount fraction is 65% sulfuric acid oxidation Graphene mixed solution, after sulfuric acid solution to be diluted is cooled to room temperature, is moved into three mouthfuls of burnings
In bottle, the microcrystalline cellulose powder of 5g is slowly added under 400r/min mixing speeds, starts timing after being well mixed, at 50 DEG C
Under bath temperature after sustained response 1.5h, 400mL distilled water terminating reactions are added.
（2）Secondly, by step（1）In the nano micro crystal cellulose that is obtained by graphene oxide auxiliary catalysis sulphuric acid hydrolysis mix
Close liquid and 10min be centrifuged under 11000r/min rotating speeds, outwell supernatant, repeat above-mentioned centrifugally operated up to upper liquid becomes cloudy,
Start to collect nano micro crystal cellulose, repeated centrifugation operation becomes clear again up to upper liquid, stops collecting.By receiving that collection is obtained
Rice microcrystal cellulose colloid is placed in the bag filter that specification is 8000~14000 is dialysed 2~3 days, and a dialyzate is changed every 2h,
Dialyzate is distilled water, finally obtains pH close to neutral Nanocrystalline Cellulose Colloid.
（3）Finally, by step（2）In neutral Nanocrystalline Cellulose Colloid freeze-drying in freeze drier for obtaining
48h, that is, obtain nano micro crystal cellulose powder.
This implementation steps（1）Middle graphite oxide is obtained through the oxidation stripping of following technique by graphite：1. 5g graphite oxides,
2.5g sodium nitrate and 60 milliliter of 98% sulfuric acid are placed in there-necked flask, and 30min is stirred at room temperature, and rotating speed is 400rpm；2. it is then placed in water
Bath, is kept for less than 20 DEG C, is slowly added to 15g potassium permanganate, controls the addition time for 0.5 hour, and 2h is stirred after adding, whole
Temperature is all controlled below 20 DEG C；3. 50mL distilled water is then added dropwise over, then is warmed up to 35 DEG C, stirring 2h；4. added after
100mL water, is warmed up to 95 DEG C, reacts 15min；5. it is 30% hydrogen peroxide to add 10mL mass fractions, reacts 10min, is taken out, plus
1000mL water dilutes；6. obtained mixed liquor is carried out into vacuum filtration, then drying obtains graphite oxide.Step（1）Middle crystallite
Cellulose powder quality is 1 with sulfuric acid volume ratio: 10；Step（2）In every time centrifuge washing add amount of distilled water for 25ml~
35ml.The yield of nano micro crystal cellulose prepared by this experiment is about 52.50%.
Embodiment 3
（1）First, the graphite oxide for taking 0.3g is placed in beaker, adds a certain amount of distilled water, is in ultrasonic power
Ultrasound is taken out after peeling off 2h in the ultrasonic cleaning instrument of 100W.The concentrated sulfuric acid for adding a certain amount of mass fraction to be 98%, is configured to matter
Amount fraction is 65% sulfuric acid oxidation Graphene mixed solution, after sulfuric acid solution to be diluted is cooled to room temperature, is moved into three mouthfuls of burnings
In bottle, the microcrystalline cellulose powder of 5g is slowly added under 400r/min mixing speeds, starts timing after being well mixed, at 50 DEG C
Under bath temperature after sustained response 1.5h, 400mL distilled water terminating reactions are added.
（2）Secondly, by step（1）In the nano micro crystal cellulose that is obtained by graphene oxide auxiliary catalysis sulphuric acid hydrolysis mix
Close liquid and 10min be centrifuged under 11000r/min rotating speeds, outwell supernatant, repeat above-mentioned centrifugally operated up to upper liquid becomes cloudy,
Start to collect nano micro crystal cellulose, repeated centrifugation operation becomes clear again up to upper liquid, stops collecting.By receiving that collection is obtained
Rice microcrystal cellulose colloid is placed in the bag filter that specification is 8000~14000 is dialysed 2~3 days, and a dialyzate is changed every 2h,
Dialyzate is distilled water, finally obtains pH close to neutral Nanocrystalline Cellulose Colloid.
（3）Finally, by step（2）In neutral Nanocrystalline Cellulose Colloid freeze-drying in freeze drier for obtaining
48h, that is, obtain nano micro crystal cellulose powder.
This implementation steps（1）Middle graphite oxide is obtained through the oxidation stripping of following technique by graphite：1. 5g graphite oxides,
2.5g sodium nitrate and 60 milliliter of 98% sulfuric acid are placed in there-necked flask, and 30min is stirred at room temperature, and rotating speed is 400rpm；2. it is then placed in water
Bath, is kept for less than 20 DEG C, is slowly added to 15g potassium permanganate, controls the addition time for 0.5 hour, and 2h is stirred after adding, whole
Temperature is all controlled below 20 DEG C；3. 50mL distilled water is then added dropwise over, then is warmed up to 35 DEG C, stirring 2h；4. added after
100mL water, is warmed up to 95 DEG C, reacts 15min；5. it is 30% hydrogen peroxide to add 10mL mass fractions, reacts 10min, is taken out, plus
1000mL water dilutes；6. obtained mixed liquor is carried out into vacuum filtration, then drying obtains graphite oxide.Step（1）Middle crystallite
Cellulose powder quality is 1 with sulfuric acid volume ratio: 10；Step（2）In every time centrifuge washing add amount of distilled water for 25ml~
35ml.The yield of nano micro crystal cellulose prepared by this experiment is about 40.20%.
Comparative example 1：
First, sulphuric acid hydrolysis cellulose：The concentrated sulfuric acid is added in distilled water first, is configured to the sulphur that mass concentration is 65%
Acid solution 50mL, sulfuric acid solution to be diluted is cooled to room temperature, moves into there-necked flask, and low whipping speed is 400r/min, temperature
Spend for 50 DEG C when be slowly added to microcrystalline cellulose powder 5g, it is well mixed after start timing, after reaction 1.5h, plus 400mL distillations
Water terminating reaction, obtains the nano micro crystal cellulose mixed liquor of sour water solution preparation.
2nd, the preparation of Nanocrystalline Cellulose Colloid：Nano microcrystalline prepared by the sour water solution that will be obtained in step one first
Cellulose mixed liquor is set to be centrifuged in the centrifuge that 11000 r/min set of time are 10min in rotating speed, outwells supernatant,
Above-mentioned centrifugally operated is repeated up to upper liquid becomes cloudy, starts to collect nano micro crystal cellulose, repeated centrifugation operation is until upper strata
Liquid becomes clear again, stops collecting.The Nanocrystalline Cellulose Colloid for obtaining will be collected and be placed in the dialysis that specification is 8000~14000
Dialysed 2~3 days in bag, dialyzate is distilled water, and a dialyzate is changed every 2h, finally obtain the nano micro crystal cellulose of neutrality
Colloid.
3rd, freeze-drying：The neutral Nanocrystalline Cellulose Colloid that will be obtained in step 2 is freezed in freeze drier
Dry, that is, obtain powdered nano micro crystal cellulose.
Microcrystalline cellulose powder quality and sulfuric acid volume ratio are 1 in step one: 10；Each centrifuge washing adds in step 2
Amount of distilled water is 25ml~35ml.The yield of nano micro crystal cellulose prepared by this experiment is 38.40%.
Table 1 is the yield of the nano micro crystal cellulose prepared with graphene oxide co-catalysis sour water solution with the oxidation stone for adding
The situation of change of the amount of black alkene, corresponds respectively to comparative example and embodiment 1, embodiment 2, embodiment 3.
| Graphene oxide addition（g） | 0 | 0.1 | 0.2 | 0.3 |
| Nano micro crystal cellulose yield（%） | 38.40 | 41.80 | 52.50 | 40.20 |
By embodiment and the results contrast of comparative example, it is seen that via the nano micro crystal cellulose of graphene oxide co-catalysis
Prepare yield higher.
Claims (6)
1. a kind of method that graphene oxide co-catalysis sour water solution prepares nano micro crystal cellulose, it is characterised in that with graphite oxide
Alkene prepares nano micro crystal cellulose for catalyst intensified acid hydrolysis, comprises the following steps that：
Step（1）First, take a certain amount of graphite oxide to be placed in beaker, add a certain amount of distilled water, be in ultrasonic power
Taken out after ultrasound is peeled off 2 hours in the ultrasonic cleaning instrument of 100W；The concentrated sulfuric acid that a certain amount of mass fraction is 98% is added, is prepared
Into the sulfuric acid oxidation Graphene mixed solution that mass fraction is 65%, sulfuric acid oxidation Graphene mixed solution to be diluted is cooled to
After room temperature, it is moved into there-necked flask, a certain amount of microcrystalline cellulose powder is slowly added under 400r/min mixing speeds, mixes
Start timing after closing uniformly, after persistently carrying out acid hydrolytic reaction certain hour under certain bath temperature, add 400mL distilled water
Terminating reaction；
Step（2）Secondly, by step（1）In the nano micro crystal cellulose that is obtained by graphene oxide co-catalysis sulphuric acid hydrolysis mix
Liquid is centrifuged 10min under 11000r/min rotating speeds, outwells supernatant, repeats above-mentioned centrifugally operated up to upper liquid becomes cloudy, and opens
Begin to collect nano micro crystal cellulose, repeated centrifugation operation becomes clear again up to upper liquid, stops collecting；The nanometer for obtaining will be collected
Microcrystal cellulose colloid is placed in the bag filter that specification is 8000~14000 and dialyses 2~3 days, changes a dialyzate every 2h, thoroughly
Analysis liquid is distilled water, finally obtains pH close to neutral Nanocrystalline Cellulose Colloid；
Step（3）Finally, by step（2）In neutral Nanocrystalline Cellulose Colloid freeze-drying in freeze drier for obtaining
48h, that is, obtain nano micro crystal cellulose powder.
2. the method that a kind of graphene oxide co-catalysis sour water solution according to claim 1 prepares nano micro crystal cellulose,
It is characterized in that step（1）Middle microcrystalline cellulose powder quality and the sulfuric acid oxidation Graphene mixed solution that mass fraction is 65%
The ratio of volume is 1:10.
3. the method that a kind of graphene oxide co-catalysis sour water solution according to claim 1 prepares nano micro crystal cellulose,
It is characterized in that step（1）Described in sour water solution low whipping speed be 400r/min, bath temperature be 50 DEG C.
4. the method that a kind of graphene oxide co-catalysis sour water solution according to claim 1 prepares nano micro crystal cellulose,
It is characterized in that step（1）In graphite oxide aoxidized through following technique for graphite：
1. 5g powdered graphites, 2.5g sodium nitrate and 60 milliliter of 98% sulfuric acid are taken to be placed in there-necked flask, is stirred at room temperature 30 minutes, turned
Speed is 400rpm；
2. it is then placed in water-bath, keeps reaction temperature below 20 DEG C, 15g potassium permanganate is slowly added to, when control is added
Between be 0.5 hour, after adding stir 2 hours, whole reaction temperature is all controlled below 20 DEG C；
3. 50 milliliters of distilled water are then added dropwise over, then are warmed up to 35 DEG C, stirring 2 hours；
4. 100 milliliters of water are disposably added after, 95 DEG C are warmed up to, continues to react 15 minutes；
5. it is 30% hydrogen peroxide to add 10mL mass fractions, and stirring is taken out after 10 minutes, plus 1000 milliliters of distilled water dilutings；
6. obtained mixed liquor is carried out into vacuum filtration, then drying obtains graphite oxide.
5. the method that a kind of graphene oxide co-catalysis sour water solution according to claim 1 prepares nano micro crystal cellulose,
It is characterized in that step（1）Described in addition graphene oxide as acid-hydrolyzed catalyst, improve sour hydrolysis efficiency, hydrolysis
Reaction time is 1.5h.
6. the method that a kind of graphene oxide co-catalysis sour water solution according to claim 1 prepares nano micro crystal cellulose,
It is characterized in that step（1）Described in graphene oxide addition quality for microcrystalline cellulose 2%~6%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510273595.2A CN104910394B (en) | 2015-05-26 | 2015-05-26 | A kind of method that graphene oxide co-catalysis sour water solution prepares nano micro crystal cellulose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510273595.2A CN104910394B (en) | 2015-05-26 | 2015-05-26 | A kind of method that graphene oxide co-catalysis sour water solution prepares nano micro crystal cellulose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104910394A CN104910394A (en) | 2015-09-16 |
| CN104910394B true CN104910394B (en) | 2017-07-04 |
Family
ID=54079871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510273595.2A Active CN104910394B (en) | 2015-05-26 | 2015-05-26 | A kind of method that graphene oxide co-catalysis sour water solution prepares nano micro crystal cellulose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104910394B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110420663B (en) * | 2019-08-15 | 2021-01-12 | 山东大学 | Composite catalyst for producing small molecular acid by efficiently catalyzing and degrading straw and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103174046A (en) * | 2013-04-11 | 2013-06-26 | 浙江理工大学 | Method for preparing nanometer microcrystalline cellulose by combining acid hydrolysis and ultrasonic treatment |
-
2015
- 2015-05-26 CN CN201510273595.2A patent/CN104910394B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103174046A (en) * | 2013-04-11 | 2013-06-26 | 浙江理工大学 | Method for preparing nanometer microcrystalline cellulose by combining acid hydrolysis and ultrasonic treatment |
Non-Patent Citations (2)
| Title |
|---|
| "Depolymerization of cellulosic feedstocks using magnetically separable functionalized graphene oxide";Deepak Verma et al.;《RSC Advances》;20130429;第3卷;第13265-13272页 * |
| "Graphene oxide for cellulose hydrolysis: how it works as a highly active catalyst?";Xiaochen Zhao et al.;《Chem. Commun.》;20140210;第50卷;第3439-3442页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104910394A (en) | 2015-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103866487B (en) | The preparation method of a kind of nano micro crystal cellulose/chitosan/polyvinyl alcohol composite nanometer film | |
| CN107915853A (en) | A kind of nano-cellulose/graphene composite and flexible film and preparation method and application | |
| CN103588190B (en) | A kind of method being prepared carbosphere by lignocellulose | |
| CN102433786B (en) | Method for preparing micro nano-crystalline cellulose with mechanical force chemical method | |
| CN105601966B (en) | A kind of nano micro crystal cellulose based conductive film preparation method | |
| CN105568730A (en) | Method for preparing renewable nano-celluloses | |
| CN103174046A (en) | Method for preparing nanometer microcrystalline cellulose by combining acid hydrolysis and ultrasonic treatment | |
| CN111116762B (en) | Preparation method of hydrophobic cellulose nanocrystals | |
| CN102633957B (en) | Preparation method of modified polymethyl-methacrylate graphene nanoribbon (PMMA-GNR) | |
| CN104445167A (en) | Preparation method of water-soluble graphene | |
| CN103882624B (en) | The preparation method of WATER RESISTANCE nano micro crystal cellulose/polyvinyl alcohol/polyacrylic acid/silica composite nano-fiber membrane | |
| CN102093484B (en) | Method for preparing nano crystal cellulose by dissociating ZnCl2 | |
| CN105174249B (en) | High-performance graphene film and fiber and its gel conversion preparation method | |
| CN103588886B (en) | A kind of Easily-water dispersible nanocrystalline cellulose and preparation method thereof | |
| CN108607518A (en) | A kind of dynamic micro motor preparation method of manganese dioxide/graphite oxide alkenyl self-powered | |
| CN104692389A (en) | Preparation of nanostructured material | |
| CN108221438A (en) | A kind of preparation method of bleached eucalyptus pulp nano-cellulose | |
| CN108264613A (en) | A kind of nanofibrils cellulose surface hydrophobically modified method | |
| CN110003509A (en) | A kind of preparation method of the graphene/nanometer fiber hybrid gel film with photothermal conversion function | |
| CN104910394B (en) | A kind of method that graphene oxide co-catalysis sour water solution prepares nano micro crystal cellulose | |
| CN106147259A (en) | The preparation method of a kind of surface hydrophobicity sheet-like fiber element and this sheet-like fiber element | |
| CN105622766B (en) | A kind of preparation method of nano micro crystal cellulose | |
| CN109485736A (en) | A method of preparing nanocrystal cellulose | |
| CN107867684B (en) | A kind of preparation method of Fluorinated graphene oxide | |
| CN109134942A (en) | A kind of transparent nanofiber element anti-bacteria paper and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20171207 Address after: 200092 room 101B, room 101B, No. 1, Zhongshan north two road, Yangpu District, Shanghai Patentee after: Shanghai Tonnor Material Science Co.,Ltd. Address before: Hangzhou City, Zhejiang province 310018 Xiasha Higher Education Park No. 2 Street No. 5 Patentee before: Zhejiang Sci-Tech University |